Photochromic Compounds

ABSTRACT

A photochromic compound is provided, which may be a pyran, an oxazine, or a fulgide. The photochromic compound has at least one substituent Q attached thereto, each Q independently being —N 3 , —CN, —COOR′, —CCR′, —C(R′)C(R′)R′, —OCOR′, —OCOOR′, —SR′, —OSO 2 R′″, and/or —CON(R′)R′, wherein each R′ is hydrogen, an unsubstituted or substituted alkyl group having from 1 to 18 carbon atoms; an unsubstituted or substituted aryl group, an unsubstituted or substituted alkene or alkyne group having from 2 to 18 carbon atoms, wherein the substituents are halo or hydroxyl and R′″ is —CF 3  or a perfluorinated alkyl group having from 2 to 18 carbon atoms The number, locations and nature of the constituents Q are dependent upon the structure of the photochromic compound.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.13/452,030, filed Apr. 20, 2012, which is a divisional of U.S. patentapplication Ser. No. 12/329,092 filed Dec. 5, 2008, which is acontinuation-in-part of U.S. patent application Ser. No. 10/846,629,filed May 17, 2004, which claims the benefit of U.S. ProvisionalApplication No. 60/484,100, filed Jul. 1, 2003, all of which are herebyspecifically incorporated by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable.

REFERENCE TO A SEQUENCE LISTING

Not applicable.

BACKGROUND

Various non-limiting embodiments disclosed herein relate generally tophotochromic compounds. Other non-limiting embodiments relate to devicesand elements made using the photochromic compounds disclosed herein.

Conventional photochromic compounds have at least two states, a firststate having a first absorption spectrum and a second state having asecond absorption spectrum that differs from the first absorptionspectrum, and are capable of switching between the two states inresponse to at least actinic radiation. Further, conventionalphotochromic compounds can be thermally reversible. That is,conventional photochromic compounds are capable of switching between afirst state and a second state in response to at least actinic radiationand reverting back to the first state in response to thermal energy. Asused herein “actinic radiation” means electromagnetic radiation, such asbut not limited to ultraviolet and visible radiation that is capable ofcausing a response. More specifically, conventional photochromiccompounds can undergo a transformation in response to actinic radiationfrom one isomer to another, with each isomer having a characteristicabsorption spectrum, and can further revert back to the first isomer inresponse to thermal energy (i.e., be thermally reversible). For example,conventional thermally reversible photochromic compounds are generallycapable of switching from a first state, for example a “clear state,” toa second state, for example a “colored state,” in response to actinicradiation and reverting back to the “clear” state in response to thermalenergy.

Dichroic compounds are compounds that are capable of absorbing one oftwo orthogonal plane polarized components of transmitted radiation morestrongly than the other. Thus, dichroic compounds are capable oflinearly polarizing transmitted radiation. As used herein, “linearlypolarize” means to confine the vibrations of the electric vector oflight waves to one direction or plane. However, although dichroicmaterials are capable of preferentially absorbing one of two orthogonalplane polarized components of transmitted radiation, if the molecules ofthe dichroic compound are not suitably positioned or arranged, no netlinear polarization of transmitted radiation will be achieved. That is,due to the random positioning of the molecules of the dichroic compound,selective absorption by the individual molecules will cancel each othersuch that no net or overall linear polarizing effect is achieved. Thus,it is generally necessary to suitably position or arrange the moleculesof the dichroic compound within another material in order to form aconventional linear polarizing element, such as a linearly polarizingfilter or lens for sunglasses.

In contrast to the dichroic compounds, it is generally not necessary toposition or arrange the molecules of conventional photochromic compoundsto form a conventional photochromic element. Thus, for example,conventional photochromic elements, such as lenses for photochromiceyewear, can be formed, for example, by spin coating a solutioncontaining a conventional photochromic compound and a “host” materialonto the surface of the lens, and suitably curing the resultant coatingor layer without arranging the photochromic compound in any particularorientation. Further, even if the molecules of the conventionalphotochromic compound were suitably positioned or arranged as discussedabove with respect to the dichroic compounds, because conventionalphotochromic compounds do not strongly demonstrate dichroism, elementsmade therefrom are generally not strongly linearly polarizing.

It would be advantageous to provide photochromic compounds that canexhibit useful photochromic and/or dichroic properties in at least onestate, and that can be used in a variety of applications to impartphotochromic and/or dichroic properties.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)

Various non-limiting embodiments of the present invention will be betterunderstood when read in conjunction with the drawings, in which:

FIG. 1 shows two average difference absorption spectra obtained for aphotochromic compound according to various non-limiting embodimentsdisclosed herein using the CELL METHOD.

FIG. 2 shows a general reaction scheme for preparing photochromiccompounds (PC) having different Q groups according to the presentinvention.

FIGS. 3 and 4 each show general reaction schemes for preparing naphtholshaving different Q groups according to the present invention.

FIG. 5 shows a reaction scheme for preparing indeno-fused naphtholsaccording to the present invention.

FIG. 6 shows a reaction scheme for preparing naphthols according to thepresent invention.

DETAILED DESCRIPTION

As used in this specification and the appended claims, the articles “a,”“an,” and “the” include plural referents unless expressly andunequivocally limited to one referent.

Additionally, for the purposes of this specification, unless otherwiseindicated, all numbers expressing quantities of ingredients, reactionconditions, and other properties or parameters used in the specificationare to be understood as being modified in all instances by the term“about.” Accordingly, unless otherwise indicated, it should beunderstood that the numerical parameters set forth in the followingspecification and attached claims are approximations. At the very least,and not as an attempt to limit the application of the doctrine ofequivalents to the scope of the claims, numerical parameters should beread in light of the number of reported significant digits and theapplication of ordinary rounding techniques.

Further, while the numerical ranges and parameters setting forth thebroad scope of the invention are approximations as discussed above, thenumerical values set forth in the Examples section are reported asprecisely as possible. It should be understood, however, that suchnumerical values inherently contain certain errors resulting from themeasurement equipment and/or measurement technique.

Various non-limiting embodiments of the invention will now be described.One non-limiting embodiment provides a thermally reversible,photochromic compound having a Q group at the position describedhereinafter and optionally a Lengthening group L also describedhereinafter. Another non-limiting embodiment provides a photochromiccompound adapted to have at least a first state and a second state,wherein the thermally reversible, photochromic compound has an averageabsorption ratio greater than 2.3 in at least one state as determinedaccording to the CELL METHOD, which is described in detail below.Further, according to various non-limiting embodiments, the thermallyreversible, photochromic compound has an average absorption ratiogreater than 2.3 in an activated state as determined according to theCELL METHOD. As used herein, the term “photochromic compound” (PC)includes thermally reversible photochromic compounds chosen fromindeno[2′,3′-3,4]naphtho[1,2-b]pyran,indeno[3′,2′-3,4]naphtho[1,2-b]pyran,thiopheno[2′,3′-3,4]naphtho[1,2-b]pyran,thiopheno[3′,2′-3,4]naphtho[1,2-b]pyran,benzothiopheno[2′,3′-3,4]naphtho[1,2-b]pyran,benzothiopheno[3′,2′-3,4]naphtho[1,2-b]pyran,furo[2′,3′-3,4]naphtho[1,2-b]pyran, furo[3′,2′-3,4]naphtho[1,2-b]pyran,benzofuro[2′,3′-3,4]naphtho[1,2-b]pyran,benzofuro[3′,2′-3,4]naphtho[1,2-b]pyran, 2H-naphtho[1,2-b]pyran,3H-naphtho[2,1-b]pyran, a benzopyran, aspiro[1,3-dihydroindole-3,3′-naphtho[2,1-b][1,4]]oxazine, aspiro[1,3-dihydroindole-2,2′-naphtho[1,2-b][1,4]]oxazine a fulgide andmixtures thereof. As used herein with respect to photochromic compounds,the term “activated state” refers to the photochromic compound whenexposed to sufficient actinic radiation to cause the at least a portionof the photochromic compound to switch states. Further, as used hereinthe term “compound” means a substance formed by the union of two or moreelements, components, Ingredients, or parts and includes, withoutlimitation, molecules and macromolecules (for example polymers oroligomers) formed by the union of two or more elements, components,ingredients, or parts.

Generally speaking, the CELL METHOD of measuring average absorptionratio of a photochromic compound involves obtaining an absorptionspectrum for the photochromic compound, in an activated or unactivedstate, in each of two orthogonal polarization directions while thephotochromic compound is at least partially aligned in an aligned liquidcrystal medium that is contained within a cell assembly. Morespecifically, the cell assembly comprises two opposing glass substratesthat are spaced apart by 20 microns+/−1 micron. The substrates aresealed along two opposite edges to form the cell. The inner surface ofeach of the glass substrates is coated with a polyimide coating, thesurface of which has been at least partially ordered by rubbing.Alignment of the photochromic compound is achieved by introducing thephotochromic compound and a liquid crystal medium into the cell assemblyand allowing the liquid crystal medium to align with the rubbedpolyimide surface. Because the photochromic compound is contained withinthe liquid crystal medium, alignment of the liquid crystal medium causesthe photochromic compound to be aligned. It will be appreciated by thoseskilled in the art that the choice of the liquid crystal medium and thetemperature used during testing can affect the measured absorptionratio. Accordingly, as set forth in more detail in the Examples, forpurposes of the CELL METHOD, absorption ratio measurements are taken atroom temperature (73° F.+/−0.5° F. or better) and the liquid crystalmedium is Licristal® E7 (which is reported to be a mixture ofcyanobiphenyl and cyanoterphenyl liquid crystal compounds).

Once the liquid crystal medium and the photochromic compound arealigned, the cell assembly is placed on an optical bench (which isdescribed in more detail in the Examples). To obtain the averageabsorption ratio in the activated state, activation of the photochromiccompound is achieved by exposing the photochromic compound to UVradiation for a time sufficient to reach a saturated or near saturatedstate (that is, a state wherein the absorption properties of thephotochromic compound do not substantially change over the interval oftime during which the measurements are made). Absorption measurementsare taken over a period of time (typically 10 to 300 seconds) at 3second intervals for light that is linearly polarized in a planeperpendicular to the optical bench (referred to as the 0° polarizationplane or direction) and light that is linearly polarized in a plane thatis parallel to the optical bench (referred to as the 90° polarizationplane or direction) in the following sequence: 0°, 90°, 90°, 0° etc. Theabsorbance of the linearly polarized light by the cell is measured ateach time interval for all of the wavelengths tested and the unactivatedabsorbance (i.e., the absorbance of the cell with the liquid crystalmaterial and the unactivated photochromic compound) over the same rangeof wavelengths is subtracted to obtain absorption spectra for thephotochromic compound in each of the 0° and 90° polarization planes toobtain an average difference absorption spectrum in each polarizationplane for the photochromic compound in the saturated or near-saturatedstate.

For example, with reference to FIG. 1, there is shown the averagedifference absorption spectrum (generally indicated 10) in onepolarization plane that was obtained for a photochromic compoundaccording to one non-limiting embodiment disclosed herein. The averageabsorption spectrum (generally indicated 11) is the average differenceabsorption spectrum obtained for the same photochromic compound in theorthogonal polarization plane.

Based on the average difference absorption spectra obtained for thephotochromic compound, the average absorption ratio for the photochromiccompound is obtained as follows. The absorption ratio of thephotochromic compound at each wavelength in a predetermined range ofwavelengths corresponding to λ_(max-vis)+/−5 nanometers (generallyindicated as 14 in FIG. 1), wherein λ_(max-vis) is the wavelength atwhich the photochromic compound had the highest average absorbance inany plane, is calculated according to the following equation:

AR_(λi) =Ab _(λi) ¹ /Ab ² _(λi)  Eq.1

-   -   wherein, AR_(λi) is the absorption ratio at wavelength λi, Ab¹        _(λi) is the average absorption at wavelength λi in the        polarization direction (i.e., 0° or 90°) having the higher        absorbance, and Ab² _(λi) is the average absorption at        wavelength λi in the remaining polarization direction. As        previously discussed, the “absorption ratio” refers to the ratio        of the absorbance of radiation linearly polarized in a first        plane to the absorbance of the same wavelength radiation        linearly polarized in a plane orthogonal to the first plane,        wherein the first plane is taken as the plane with the highest        absorbance.

The average absorption ratio (‘AR’) for the photochromic compound isthen calculated by averaging the individual absorption ratios obtainedfor the wavelengths within the predetermined range of wavelengths (i.e.,λ_(max-vis)+/−5 nanometers) according to the following equation:

AR=(ΣAR_(λi))/n _(i)  Eq. 2

-   -   wherein, AR is average absorption ratio for the photochromic        compound, AR_(λi) are the individual absorption ratios (as        determined above in Eq. 1) for each wavelength within the        predetermined the range of wavelengths (i.e., λ_(max-vis)+/−5        nanometers), and n_(i) is the number of individual absorption        ratios averaged.

As previously discussed, conventional thermally reversible photochromiccompounds are adapted to switch from a first state to a second state inresponse to actinic radiation, and to revert back to the first state inresponse to thermal energy. More specifically, conventional thermallyreversible, photochromic compounds are capable of transforming from oneisomeric form (for example and without limitation, a closed form) toanother isomeric form (for example and without limitation, an open form)in response to actinic radiation, and reverting back to the closed formwhen exposed to thermal energy. However, as previously discussed,generally conventional thermally reversible photochromic compounds donot strongly demonstrate dichroism.

As discussed above, non-limiting embodiments disclosed herein provide athermally reversible photochromic compound having an average absorptionratio greater than 2.3 in at least one state as determined according toCELL METHOD and/or a thermally reversible photochromic compound that canbe used as an intermediate in the preparation of a photochromic compoundhaving an absorption ratio greater than 2.3. Thus, the thermallyreversible photochromic compound according to this non-limitingembodiment can display useful photochromic properties and/or usefulphotochromic and dichroic properties. That is, the thermally reversible,photochromic compound can be a thermally reversible, photochromic and/orphotochromic-dichroic compound. As used herein with respect to thephotochromic compounds described herein, the term“photochromic-dichroic” means displaying both photochromic and dichroicproperties under certain conditions, which properties are at leastdetectable by instrumentation.

According to other non-limiting embodiments, the thermally reversiblephotochromic compounds can be thermally reversible photochromic-dichroiccompounds having an average absorption ratio ranging from 4 to 20, from3 to 30, or from 2.5 to 50 in at least one state as determined accordingto CELL METHOD. It will be appreciated by those skilled in the art thatthe higher the average absorption ratio of the photochromic compound themore linearly polarizing the photochromic compound will be. Therefore,according to various non-limiting embodiments, the thermally reversiblephotochromic compounds can have any average absorption ratio required toachieve a desired level of linear polarization.

Another non-limiting embodiment provides a thermally reversible,photochromic compound that is free of oxazines and adapted to have atleast a first state and a second state, wherein the photochromiccompound has an average absorption ratio of at least 1.5 in at least onestate as determined according to CELL METHOD. Further, according to thisnon-limiting embodiment, the average average absorption ratio can rangefrom 1.5 to 50 in at least one state as determined according to CELLMETHOD.

In particular embodiments of the present invention, a photochromicmaterial is provided comprising an indeno[2′,3′-3,4]naphtho[1,2-b]pyran,indeno[3′,2′-3,4]naphtho[1,2-b]pyran,thiopheno[2′,3′-3,4]naphtho[1,2-b]pyran,thiopheno[3′,2′-3,4]naphtho[1,2-b]pyran,benzothiopheno[2′,3′-3,4]naphtho[1,2-b]pyran,benzothiopheno[3′,2′-3,4]naphtho[1,2-b]pyran,furo[2′,3′-3,4]naphtho[1,2-b]pyran, furo[3′,2′-3,4]naphtho[1,2-b]pyran,benzofuro[2′,3′-3,4]naphtho[1,2-b]pyran,benzofuro[3′,2′-3,4]naphtho[1,2-b]pyran, 2H-naphtho[1,2-b]pyran,3H-naphtho[2,1-b]pyran, a benzopyran, aspiro[1,3-dihydroindole-3,3′-naphtho[2,1-b][1,4]]oxazine, aspiro[1,3-dihydroindole-2,2′-naphtho[1,2-b][1,4]]oxazine or a fulgide;wherein:

-   -   (A) said photochromic material has at least one substituent Q        attached thereto at the specific carbon atoms named hereinafter,        each Q independently comprising —N₃, —CN, —COOR′, —CCR′,        —C(R′)C(R′)R′, —OCOR′, —OCOOR′, —SR′, —OSO₂R′″, and/or        —CON(R′)R′, wherein each R′ independently comprises hydrogen, an        unsubstituted or substituted alkyl group having from 1 to 18        carbon atoms, an unsubstituted or substituted aryl group, an        unsubstituted or substituted alkene or alkyne group having from        2 to 18 carbon atoms, wherein said substituents are chosen from        halo and hydroxyl and R′″ comprises —CF₃ or a perfluorinated        alkyl group having from 2 to 18 carbon atoms; provided wherein:        -   (a) when said photochromic material comprises an            indeno[2′,3′-3,4]naphtho[1,2-b]pyran,            indeno[3′,2′-3,4]naphtho[1,2-b]pyran,            thiopheno[3′,2′-3,4]naphtho[1,2-b]pyran,            thiopheno[3′,2′-3,4]naphtho[1,2-b]pyran,            benzothiopheno[2′,3′-3,4]naphtho[1,2-b]pyran,            benzothiopheno[3′,2′-3,4]naphtho[1,2-b]pyran,            furo[2′,3′-3,4]naphtho[1,2-b]pyran,            furo[3′,2′-3,4]naphtho[1,2-b]pyran,            benzofuro[2′,3′-3,4]naphtho[1,2-b]pyran,            benzofuro[3′,2′-3,4]naphtho[1,2-b]pyran, Q is attached            thereto at the 7- and/or 10-positions and comprises —N₃,            —COOR′, —CCR′, —C(R′)C(R′)R′, —OCOR′, —OCOOR′, —SR′,            —OSO₂R′″ or —CN, provided that when said photochromic            material is an indeno[2′,3′-3,4]naphtho[1,2-b]pyran said            material compound is substantially free of substituents at            the 12-position;        -   (b) when said photochromic material comprises a            3H-naphtho[2,1-b]pyran, Q is attached thereto at the 6-            and/or 7-positions and independently comprises for each            occurrence, —N₃ or —OCOOR′;        -   (c) when said photochromic material comprises a            2H-naphtho[1,2-b]pyran, Q is attached thereto at the            8-position and comprises —N₃; or —OCOOR′, provided that said            photochromic material is substantially free of substituents            at the 5-position;        -   (d) when said photochromic material comprises a benzopyran,            Q is attached thereto at the 7-position and comprises —N₃,            —CN, —CCR′, or —OSO₂R′″;        -   (e) when said photochromic material comprises a            spiro[1,3-dihydroindole-2,2′-naphtho[1,2-b][1,4]]oxazine,            substituents Q are attached thereto at the 5-, 6- and/or            8′-positions and independently comprise for each occurrence            —N₃; —CCR′, provided that the indolino group is            substantially free of N-substituents; or —OSO₂R′″, provided            that said photochromic material is substantially free of            carbonyl groups;        -   (f) when said photochromic material comprises a            spiro[1,3-dihydroindole-2,3′-naphtho[2,1-b][1,4]]oxazine,            substituents Q are attached thereto at the 5-, 6-, 6′ and/or            7′-positions and independently comprise for each occurrence            —N₃; —CCR′, provided that the indolino group is            substantially free of N-substituents; or —OSO₂R′″, provided            that said photochromic material is substantially free of            carbonyl groups; and        -   (g) when said photochromic material comprises a fulgide, Q            comprises —N₃, —CN, —CCR′, or —OSO₂R′″; and    -   (B) optionally, said photochromic material has at least one        lengthening agent L represented by the following formula (which        is described in detail below):

—[S₁]_(c)-[Q₁-[S₂]_(d)]_(d′)-[Q₂-[S₃]_(e)]_(e′)-[Q₃-[S₄]_(f)]_(f′)—S₅—P

As used herein, the term “attached” means directly bonded to orindirectly bonded to through another group. Thus, for example, accordingto various non-limiting embodiments disclosed herein, L can be directlybonded to PC as a substituent on PC, or L can be a substituent onanother group (such as a group represented by R, which is discussedbelow) that is directly bonded to PC (i.e., L is indirectly bonded toPC). Although not limiting herein, according to various non-limitingembodiments, L can be attached to PC so as to extend or lengthen PC inan activated state such that the absorption ratio of the extended PC(i.e., the photochromic compound) is enhanced as compared to PC alone.Although not limiting herein, according to various non-limitingembodiments, the location of attachment of L on PC can be chosen suchthat L lengthens PC in at least one of a direction parallel to or adirection perpendicular to a theoretical transitional dipole moment ofthe activated form of PC. Regarding the position of L, it may besubsequently attached to the photochromic compound at the location ofthe Q group. The photochromic compound of the present invention can haveat least one Q group at the position(s) indicated and optionally one ormore L groups. As used herein the term “theoretical transitional dipolemoment” refers to transient dipolar polarization created by interactionof electromagnetic radiation with the molecule. See, for example, IUPACCompendium of Chemical Technology, 2^(nd) Ed., International Union ofPure and Applied Chemistry (1997).

With reference to L above, each Q₁, Q₂, and Q₃ can be independentlychosen for each occurrence from: a divalent group chosen from: anunsubstituted or a substituted aromatic group, an unsubstituted or asubstituted alicyclic group, an unsubstituted or a substitutedheterocyclic group, and mixtures thereof, wherein substituents arechosen from: a group represented by P, liquid crystal mesogens, halogen,poly(C₁-C₁₈ alkoxy), C₁-C₁₈ alkoxycarbonyl, C₁-C₁₈ alkylcarbonyl, C₁-C₁₈alkoxycarbonyloxy, aryloxycarbonyloxy, perfluoro(C₁-C₁₈)alkoxy,perfluoro(C₁-C₁₈)alkoxycarbonyl, perfluoro(C₁-C₁₈)alkylcarbonyl,perfluoro(C₁-C₁₈)alkylamino, di-(perfluoro(C₁-C₁₈)alkyl)amino,perfluoro(C₁-C₁₈)alkylthio, C₁-C₁₈ alkylthio, C₁-C₁₈ acetyl, C₃-C₁₀cycloalkyl, C₃-C₁₀ cycloalkoxy, a straight-chain or branched C₁-C₁₈alkyl group that is mono-substituted with cyano, halo, or C₁-C₁₈ alkoxy,or poly-substituted with halo, and a group comprising one of thefollowing formulae: -M(T)_((t-1)), and -M(OT)_((t-1)), wherein M ischosen from aluminum, antimony, tantalum, titanium, zirconium andsilicon, T is chosen from organofunctional radicals, organofunctionalhydrocarbon radicals, aliphatic hydrocarbon radicals and aromatichydrocarbon radicals, and t is the valence of M. As used herein, theprefix “poly” means at least two.

As discussed above, Q₁, Q₂, and Q₃ can be independently chosen for eachoccurrence from a divalent group, such as an unsubstituted or asubstituted aromatic group, unsubstituted or substituted heterocyclicgroup, and an unsubstituted or substituted alicylic group. Non-limitingexamples of useful aromatic groups include: benzo, naphtho, phenanthro,biphenyl, tetrahydro naphtho, terphenyl, and anthraceno.

As used herein the term “heterocyclic group” means a compound having aring of atoms, wherein at least one atom forming the ring is differentthan the other atoms forming the ring. Further, as used herein, the termheterocyclic group specifically excludes fused heterocyclic groups.Non-limiting examples of suitable heterocyclic groups from which Q₁, Q₂,and Q₃ can be chosen include: isosorbitol, dibenzofuro, dibenzothieno,benzofuro, benzothieno, thieno, furo, dioxino, carbazolo, anthranilyl,azepinyl, benzoxazolyl, diazepinyl, dioazlyl, imidazolidinyl,imidazolyl, imidazolinyl, indazolyl, indoleninyl, indolinyl,indolizinyl, indolyl, indoxazinyl, isobenzazolyl, isoindolyl,isooxazolyl, isooxazyl, isopyrroyl, isoquinolyl, isothiazolyl,morpholino, morpholinyl, oxadiazolyl, oxathiazolyl, oxathiazyl,oxathiolyl, oxatriazolyl, oxazolyl, piperazinyl, piperazyl, piperidyl,purinyl, pyranopyrrolyl, pyrazinyl, pyrazolidinyl, pyrazolinyl,pyrazolyl, pyrazyl, pyridazinyl, pyridazyl, pyridyl, pyrimidinyl,pyrimidyl, pyridenyl, pyrrolidinyl, pyrrolinyl, pyrroyl, quinolizinyl,quinuclidinyl, quinolyl, thiazolyl, triazolyl, triazyl,N-arylpiperazino, aziridino, arylpiperidino, thiomorpholino,tetrahydroquinolino, tetrahydroisoquinolino, pyrryl, unsubstituted,mono- or di-substituted C₄-C₁₈ spirobicyclic amines, and unsubstituted,mono- or di-substituted C₄-C₁₈ spirotricyclic amines.

As discussed above, according to various non-limiting embodiments Q₁,Q₂, and Q₃ can be chosen from mono- or di-substituted C₄-C₁₈spirobicyclic amine and C₄-C₁₈ spirotricyclic amine. Non-limitingexamples of suitable substituents include aryl, C₁-C₆ alkyl, C₁-C₆alkoxy or phenyl (C₁-C₆)alkyl. Specific non-limiting examples of mono-or di-substituted spirobicyclic amines include:2-azabicydo[2.2.1]hept-2-yl; 3-azabicyclo[3.2.1]oct-3-yl;2-azabicyclo[2.2.2]oct-2-yl; and 6-azabicyclo[3.2.2]nonan-6-yl. Specificnon-limiting examples of mono- or di-substituted tricyclic aminesinclude: 2-azatricyclo[3.3.1.1(3,7)]decan-2-yl;4-benzyl-2-azatricydo[3.3.1.1 (3,7)]decan-2-yl;4-methoxy-6-methyl-2-azatricyclo[3.3.1.1 (3,7)]decan-2-yl;4-azatricydo[4.3.1.1(3,8)]undecan-4-yl; and7-methyl-4-azatricyclo[4.3.1.1(3,8)]undecan-4-yl.

Examples of alicyclic groups from which Q₁, Q₂, and Q₃ can be choseninclude, without limitation, cyclohexyl, cyclopropyl, norbomenyl,decalinyl, adamantanyl, bicyclooctane, per-hydrofluorene, and cubanyl.

With continued reference to L, each S₁, S₂, S₃, S₄, and S₅ isindependently chosen for each occurrence from a spacer unit chosen from:

-   -   (1) —(CH₂)_(g), —(CF₂)_(h)—, —Si(CH₂)_(g)—, —(Si[(CH₃)₂]O)_(h)—,        wherein g is independently chosen for each occurrence from 1 to        20; h is chosen from 1 to 16 inclusive;    -   (2) —N(Z)—, —C(Z)═C(Z)—, —C(Z)═N—, —C(Z′)—C(Z′)—, or a single        bond, wherein Z is independently chosen for each occurrence from        hydrogen, C₁-C₆ alkyl, C₃-C₁₀ cycloalkyl and aryl, and Z′ is        independently chosen for each occurrence from C₁-C₁₈ alkyl,        C₃-C₁₀ cycloalkyl and aryl; and    -   (3) —O—, —C(O)—, —C≡C—, —N═N—, —S—, —S(O)—, —S(O)(O)—,        —(O)S(O)O—, —O(O)S(O)O— straight-chain or branched C₁-C₂₄        alkylene residue, said C₁-C₂₄ alkylene residue being        unsubstituted, mono-substituted by cyano or halo, or        poly-substituted by halo; provided that when two spacer units        comprising heteroatoms are linked together the spacer units are        linked so that heteroatoms are not directly linked to each other        and when S₁ and S₅ are linked to PC and P, respectively, they        are linked so that two heteroatoms are not directly linked to        each other. As used herein the term “heteroatom” means atoms        other than carbon or hydrogen.

According to various non-limiting embodiments disclosed herein, in L, c,d, e, and f each can be independently chosen from an integer rangingfrom 1 to 20, inclusive; and d′, e′ and f′ each can be independentlychosen from 0, 1, 2, 3, and 4, provided that the sum of d′+e′+f′ is atleast 1. According to other non-limiting embodiments disclosed herein,c, d, e, and f each can be independently chosen from an integer rangingfrom 0 to 20, inclusive; and d′, e′ and f′ each can be independentlychosen from 0, 1, 2, 3, and 4, provided that the sum of d′+e′+f′ is atleast 2. According to still other non-limiting embodiments disclosedherein, c, d, e, and f each can be independently chosen from an integerranging from 0 to 20, inclusive; and d′, e′ and f′ each can beindependently chosen from 0, 1, 2, 3, and 4, provided that the sum ofd′+e′+f′ is at least 3. According to still other non-limitingembodiments disclosed herein, c, d, e, and f each can be independentlychosen from an integer ranging from 0 to 20, inclusive; and d′, e′ andf′ each can be independently chosen from 0, 1, 2, 3, and 4, providedthat the sum of d′+e′+f′ is at least 1.

Further, in L, P can be chosen from: hydroxy, amino, C₂-C₁₈ alkenyl,C₂-C₁₈ alkynyl, azido, silyl, siloxy, silylhydride,(tetrahydro-2H-pyran-2-yl)oxy, thio, isocyanato, thioisocyanato,acryloyloxy, methacryloyloxy, 2-(acryloyloxy)ethylcarbamyl,2-(methacryloyloxy)ethylcarbamyl, azindinyl, allyloxycarbonyloxy, epoxy,carboxylic acid, carboxylic ester, acryloylamino, methacryloylamino,aminocarbonyl, C₁-C₁₈ alkyl aminocarbonyl, aminocarbonyl(C₁-C₁₈)alkyl,C₁-C₁₈ alkyloxycarbonyloxy, halocarbonyl, hydrogen, aryl,hydroxy(C₁-C₁₈)alkyl, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, amino(C₁-C₁₈)alkyl,C₁-C₁₈ alkylamino, di-(C₁-C₁₈)alkylamino, C₁-C₁₈ alkyl(C₁-C₁₈)alkoxy,C₁-C₁₈ alkoxy(C₁-C₁₈)alkoxy, nitro, poly(C₁-C₁₈)alkyl ether,(C₁-C₁₈)alkyl(C₁-C₁₈)alkoxy(C₁-C₁₈)alkyl, polyethyleneoxy,polypropyleneoxy, ethylenyl, acryloyl, acryloyloxy(C₁-C₁₈)alkyl,methacryloyl, methacryloyloxy(C₁-C₁₈)alkyl, 2-chioroacryloyl,2-phenylacryloyl, acryloyloxyphenyl, 2-chloroacryloylamino,2-phenylacryloylaminocarbonyl, oxetanyl, glycidyl, cyano,isocyanato(C₁-C₁₈)alkyl, itaconic acid ester, vinyl ether, vinyl ester,a styrene derivative, main-chain and side-chain liquid crystal polymers,siloxane derivatives, ethyleneimine derivatives, maleic acidderivatives, fumaric acid derivatives, unsubstituted cinnamic acidderivatives, cinnamic acid derivatives that are substituted with atleast one of methyl, methoxy, cyano and halogen, or substituted orunsubstituted chiral or non-chiral monovalent or divalent groups chosenfrom steroid radicals, terpenoid radicals, alkaloid radicals andmixtures thereof, wherein the substituents are independently chosen fromC₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, amino, C₃-C₁₀ cycloalkyl, C₁-C₁₈alkyl(C₁-C₁₈)alkoxy, fluoro(C₁-C₁₈)alkyl, cyano, cyano(C₁-C₁₈)alkyl,cyano(C₁-C₁₈)alkoxy or mixtures thereof, or P is a structure having from2 to 4 reactive groups or P is an unsubstituted or substituted ringopening metathesis polymerization precursor.

According to various non-limiting embodiments disclosed herein, when Pis a polymerizable group, the polymerizable group can be any functionalgroup adapted to participate in a polymerization reaction. Non-limitingexamples of polymerization reactions include those described in thedefinition of “polymerization” in Hawley's Condensed Chemical DictionaryThirteenth Edition, 1997, John Wiley & Sons, pages 901-902, whichdisclosure is incorporated herein by reference. For example, althoughnot limiting herein, polymerization reactions include: “additionpolymerization,” in which free radicals are the initiating agents thatreact with the double bond of a monomer by adding to it on one side atthe same time producing a new free electron on the other side;“condensation polymerization,” in which two reacting molecules combineto form a larger molecule with elimination of a small molecule, such asa water molecule; and “oxidative coupling polymerization.” Further,non-limiting examples of polymerizable groups include hydroxy, acryloxy,methacryloxy, 2-(acryloxy)ethylcarbamyl, 2-(methacryloxy)ethylcarbamyl,isocyanate, aziridine, allylcarbonate, and epoxy, e.g., oxiranylmethyl.

According to one specific, non-limiting embodiment, P can be chosen froma main-chain or a side-chain liquid crystal polymer and a liquid crystalmesogen. As used herein, the term liquid crystal “mesogen” means rigidrod-like or disc-like liquid crystal molecules. Further, as used hereinthe term “main-chain liquid crystal polymer” refers to a polymer havingliquid crystal mesogens within the backbone (i.e., the main chain)structure of the polymer. As used herein the term “side-chain liquidcrystal polymer” refers to a polymer having liquid crystal mesogensattached to the polymer at the side chains. Although not limitingherein, generally, the mesogens are made up of two or more aromaticrings that restrict the movement of a liquid crystal polymer. Examplesof suitable rod-like liquid crystal mesogens include without limitation:substituted or unsubstituted aromatic esters, substituted orunsubstituted linear aromatic compounds, and substituted orunsubstituted terphenyls.

According to another specific, non-limiting embodiment, P can be chosenfrom a steroid radical, for example and without limitation, acholesterolic compound.

As is discussed above, various non-limiting embodiments disclosed hereinprovide a photochromic compound comprising (a) a photochromic group (PC)and (b) at least one Q group at the position described herein andoptionally at least one lengthening agent (L) (above) attached to PC.

In alternative embodiments, the photochromic compound may be representedby the following graphic formula I, II, III, IVA, IVB, V or VI:

-   -   wherein:        -   (A) each substituent Q independently comprises —N₃, —CN,            —COOR′, —CCR′, —OCOR′, —OCOOR′, —SR′, —OSO₂R′″, and/or            —CONHR′, wherein each R′ comprises hydrogen, an            unsubstituted or substituted alkyl group having from 1 to 18            carbon atoms, an unsubstituted or substituted aryl group, an            unsubstituted or substituted alkene or alkyne group having            from 2 to 18 carbon atoms, wherein said substituents are            chosen from halo and hydroxyl and R′″ comprises —CF₃ or a            perfluorinated alkyl group having from 2 to 18 carbon atoms;        -   (B) each i is an integer chosen from 0 to the total number            of available positions and each R is independently chosen            for each occurrence from:            -   (a) a group represented by B described hereinafter,            -   (b) —C(O)X₂₄, wherein X₂₄ is chosen from a lengthening                agent L, hydroxy, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, phenyl                that is unsubstituted or mono-substituted with C₁-C₁₈                alkyl or C₁-C₁₈ alkoxy, amino that is unsubstituted,                mono- or di-substituted with at least one of C₁-C₁₈                alkyl, phenyl, benzyl, and naphthyl;            -   (c) —OX₇ and —N(X₇)₂; wherein X₇ is chosen from:                -   (i) a lengthening agent L, hydrogen, C₁-C₁₈ alkyl,                    C₁-C₁₈ acyl, phenyl(C₁-C₁₈)alkyl, mono(C₁-C₁₈)alkyl                    substituted phenyl(C₁-C₁₈)alkyl, mono(C₁-C₁₈)alkoxy                    substituted phenyl(C₁-C₁₈)alkyl; C₁-C₁₈                    alkoxy(C₁-C₁₈)alkyl; C₃-C₁₀ cycloalkyl;                    mono(C₁-C₁₈)alkyl substituted C₃-C₁₀ cycloalkyl,                    C₁-C₁₈ haloalkyl, allyl, benzoyl, mono-substituted                    benzoyl, naphthoyl or mono-substituted naphthoyl,                    wherein each of said benzoyl and naphthoyl                    substituents are independently chosen from C₁-C₁₈                    alkyl, and C₁-C₁₈ alkoxy;                -   (ii) —CH(X₈)X₉, wherein X₈ is chosen from a                    lengthening agent L, hydrogen or C₁-C₁₈ alkyl; and                    X₉ is chosen from a lengthening agent L, —CN, —CF₃,                    or —COOX₁₀, wherein X₁₀ is chosen from a lengthening                    agent L, hydrogen or C₁-C₁₈ alkyl;                -   (iii) —C(O)X₆, wherein X₆ is chosen from at least                    one of: a lengthening agent L, hydrogen, C₁-C₁₈                    alkoxy, phenoxy that is unsubstituted, mono- or                    di-substituted with C₁-C₁₈ alkyl or C₁-C₁₈ alkoxy,                    an aryl group that is unsubstituted, mono- or                    di-substituted with C₁-C₁₈ alkyl or C₁-C₁₈ alkoxy,                    an amino group that is unsubstituted, mono- or                    di-substituted with C₁-C₁₈ alkyl, and a phenylamino                    group that is unsubstituted, mono- or di-substituted                    with C₁-C₁₈ alkyl or C₁-C₁₈ alkoxy; or                -   (iv) tri(C₁-C₁₈)alkylsilyl,                    tri(C₁-C₁₈)alkylsilyloxy, tri(C₁-C₁₈)alkoxysilyl,                    tri(C₁-C₁₈)alkoxysilyloxy, di(C₁-C₁₈)alkyl(C₁-C₁₈                    alkoxy)silyl, di(C₁-C₁₈)alkyl(C₁-C₁₈                    alkoxy)silyloxy, di(C₁-C₁₈)alkoxy(C₁-C₁₈ alkyl)silyl                    or di(C₁-C₁₈)alkoxy(C₁-C₁₈ alkyl)silyloxy;            -   (d) —SX₁₁; wherein X₁₁ is chosen from a lengthening                agent L, hydrogen, C₁-C₁₈ alkyl, C₁-C₁₈ haloalkyl, an                aryl group that is unsubstituted, or mono- or                di-substituted with C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, or                halogen;            -   (e) a nitrogen containing ring represented by Formula i:

-   -   wherein        -   (i) n is an integer chosen from 0, 1, 2, and 3, provided            that if n is 0, U′ is U, and each U is independently chosen            for each occurrence from —CH₂—, —CH(X₁₂)—, —C(X₁₂)₂—,            —CH(X₁₃)—, —C(X₁₃)₂—, and —C(X₁₂)(X₁₃)—, wherein X₁₂ is            chosen from a lengthening agent L and C₁-C₁₂ alkyl, and X₁₃            is chosen from a lengthening agent L, phenyl and naphthyl,            and        -   (ii) U′ is chosen from U, —O—, —S—, —S(O)—, —NH—, —N(X₁₂)—            or —N(X₁₃)—, and m is an integer chosen from 1, 2, and 3;        -   (f) the group represented by Formula ii or iii;

-   -   wherein X₁₄, X₁₅, and X₁₆ are independently chosen for each        occurrence from a lengthening agent L, hydrogen, C₁-C₁₈ alkyl,        phenyl or naphthyl, or X₁₄ and X₁₅ together form a ring of 5 to        8 carbon atoms; p is an integer chosen from 0, 1, or 2, and X₁₇        is independently chosen for each occurrence from a lengthening        agent L, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, or halogen;        -   (g) immediately adjacent R groups together form a group            represented by Formula vii, viii, or ix:

-   -   wherein        -   (i) W and W′ are independently chosen for each occurrence            from —O—, —N(X₇)—, —C(X₁₄)—, and —C(X₁₇)—;        -   (ii) X₁₄, X₁₅ and X₁₇, wherein X₁₄, and X₁₈ are            independently chosen for each occurrence from a lengthening            agent L, hydrogen, C₁-C₁₈ alkyl, phenyl or naphthyl, or X₁₄            and X₁₅ together form a ring of 5 to 8 carbon atoms; and X₁₇            is independently chosen for each occurrence from a            lengthening agent L, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, or            halogen; and        -   (iii) q is an integer chosen from 0, 1, 2, 3, and 4; and        -   (h) a lengthening agent L represented by:

[S₁]_(c)-[Q₁-[S₂]_(d)]_(d′)-[Q₂-S₃]_(e)]_(e′)-[Q₃-[S₄]_(f)]_(f′)—S₅—Pwherein:

-   -   (i) each Q₁, Q₂, and Q₃ is independently chosen for each        occurrence from: a divalent group chosen from: an unsubstituted        or a substituted aromatic group, an unsubstituted or a        substituted alicyclic group, an unsubstituted or a substituted        heterocyclic group, and mixtures thereof, wherein substituents        are chosen from: a group represented by P, liquid crystal        mesogens, halogen, poly(C₁-C₁₈ alkoxy), C₁-C₁₈ alkoxycarbonyl,        C₁-C₁₈ alkylcarbonyl, C₁-C₁₈ alkoxycarbonyloxy,        aryloxycarbonyloxy, perfluoro(C₁-C₁₈)alkoxy,        perfluoro(C₁-C₁₈)alkoxycarbonyl, perfluoro(C₁-C₁₈)alkylcarbonyl,        perfluoro(C₁-C₁₈)alkylamino, di-(perfluoro(C₁-C₁₈)alkyl)amino,        perfluoro(C₁-C₁₈)alkylthio, C₁-C₁₈ alkylthio, C₁-C₁₈ acetyl,        C₃-C₁₀ cycloalkyl, C₃-C₁₀ cycloalkoxy, a straight-chain or        branched C₁-C₁₈ alkyl group that is mono-substituted with cyano,        halo, or C₁-C₁₈ alkoxy, or poly-substituted with halo, and a        group comprising one of the following formulae: -M(T)_((t-1))        and -M(OT)_((t-1)), wherein M is chosen from aluminum, antimony,        tantalum, titanium, zirconium and silicon, T is chosen from        organofunctional radicals, organofunctional hydrocarbon        radicals, aliphatic hydrocarbon radicals and aromatic        hydrocarbon radicals, and t is the valence of M;    -   (ii) c, d, e, and f are each independently chosen from an        integer ranging from 0 to 20, inclusive; and each S₁, S₂, S₃,        S₄, and S₅ is independently chosen for each occurrence from a        spacer unit chosen from:        -   (1) —(CH₂)_(g)—, —(CF₂)_(h)—, —Si(CH₂)_(g)—,            —(Si[(CH₃)₂]O)_(h)—, wherein g is independently chosen for            each occurrence from 1 to 20; h is a whole number from 1 to            16 inclusive;        -   (2) —N(Z)—, —C(Z)═C(Z)—, —C(Z)═N—, —C(Z′)—C(Z′)— or a single            bond, wherein Z is independently chosen for each occurrence            from hydrogen, C₁-C₁₈ alkyl, C₃-C₁₀ cycloalkyl and aryl, and            Z′ is independently chosen for each occurrence from C₁-C₁₈            alkyl, C₃-C₁₀ cycloalkyl and aryl; and        -   (3) —O—, —C(O)—, —C≡C—, —N═N—, —S—, —S(O)—, —S(O)(O)—,            —(O)S(O)—, —(O)S(O)O—, —O(O)S(O)O—, or straight-chain or            branched C₁-C₂₄ alkylene residue, said C₁-C₂₄ alkylene            residue being unsubstituted, mono-substituted by cyano or            halo, or poly-substituted by halo; provided that when two            spacer units comprising heteroatoms are linked together the            spacer units are linked so that heteroatoms are not directly            linked to each other and when S₁ and S₅ are linked to PC and            P, respectively, they are linked so that two heteroatoms are            not directly linked to each other;    -   (iii) P is chosen from: hydroxy, amino, C₂-C₁₈ alkenyl, C₂-C₁₈        alkynyl, azido, silyl, siloxy, silylhydride,        (tetrahydro-2H-pyran-2-yl)oxy, thio, isocyanato, thioisocyanato,        acryloyloxy, methacryloyloxy, 2-(acryloyloxy)ethylcarbamyl,        2-(methacryloyloxy)ethylcarbamyl, aziridinyl,        allyloxycarbonyloxy, epoxy, carboxylic acid, carboxylic ester,        acryloylamino, methacryloylamino, aminocarbonyl, C₁-C₁₈ alkyl        aminocarbonyl, aminocarbonyl(C₁-C₁₈)alkylene, C₁-C₁₈        alkyloxycarbonyloxy, halocarbonyl, hydrogen, aryl,        hydroxy(C₁-C₁₈)alkyl, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy,        amino(C₁-C₁₈)alkylene, C₁-C₁₈ alkylamino, di-(C₁-C₁₈)alkylamino,        C₁-C₁₈ alkyl(C₁-C₁₈)alkoxy, C₁-C₁₈ alkoxy(C₁-C₁₈)alkoxy, nitro,        poly(C₁-C₁₈)alkyl ether,        (C₁-C₁₈)alkyl(C₁-C₁₈)alkoxy(C₁-C₁₈)alkylene, polyethyleneoxy,        polypropyleneoxy, ethylenyl, acryloyl,        acryloyloxy(C₁-C₁₈)alkylene, methacryloyl,        methacryloyloxy(C₁-C₁₈)alkylene, 2-chloroacryloyl,        2-phenylacryloyl, acryloylphenylene, 2-chloroacryloylamino,        2-phenylacryloylamino-carbonyl, oxetanyl, glycidyl, cyano,        isocyanato(C₁-C₁₈)alkyl, itaconic acid ester, vinyl ether, vinyl        ester, a styrene derivative, main-chain and side-chain liquid        crystal polymers, siloxane derivatives, ethyleneimine        derivatives, maleic acid derivatives, fumaric acid derivatives,        unsubstituted cinnamic acid derivatives, cinnamic acid        derivatives that are substituted with at least one of methyl,        methoxy, cyano and halogen, or substituted or unsubstituted        chiral or non-chiral monovalent or divalent groups chosen from        steroid radicals, terpenoid radicals, alkaloid radicals and        mixtures thereof, wherein the substituents are independently        chosen from C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, amino, C₃-C₁₀        cycloalkyl, C₁-C₁₈ alkyl(C₁-C₁₈)alkoxy, fluoro(C₁-C₁₈)alkyl,        cyano, cyano(C₁-C₁₈)alkyl, cyano(C₁-C₁₈)alkoxy or mixtures        thereof, or P is a structure having from 2 to 4 reactive groups        or P is an unsubstituted or substituted ring opening metathesis        polymerization precursor, and    -   (iv) d′, e′ and f′ are each independently chosen from 0, 1, 2,        3, and 4, provided that a sum of d′+e′+f′ is at least 1;

(C) provided that when said photochromic material is represented bygraphic formula I:

-   -   (a) Q comprises —CN, and said photochromic material of graphic        formula I is substantially free of substituents at the        12-position, or Q comprises —N₃, —COOR′, —CCR′, —C(R′)C(R′)R′,        —OCOR′, —OCOOR′, —SR′, and —OSO₂R′″;    -   (b) the group A represents indeno, thiopheno, benzothiopheno,        furo or benzofuro; and    -   (c) B and B′ are each independently chosen from:        -   (i) hydrogen, C₁-C₁₈ alkyl, C₂-C₁₈ alkylidene, C₂-C₁₈            alkylidyne, vinyl, C₃-C₁₀ cycloalkyl, C₁-C₁₈ haloalkyl,            allyl, halogen, and benzyl that is unsubstituted or            mono-substituted with at least one of C₁-C₁₈ alkyl and            C₁-C₁₈ alkoxy;        -   (ii) phenyl that is mono-substituted at the para position            with at least one substituent chosen from: C₁-C₁₈ alkoxy,            linear or branched chain C₁-C₂₀ alkylene, linear or branched            chain C₁-C₄ polyoxyalkylene, cyclic C₃-C₂₀ alkylene,            phenylene, naphthylene, C₁-C₁₈ alkyl substituted phenylene,            mono- or poly-urethane(C₁-C₂₀)alkylene, mono- or            poly-ester(C₁-C₂₀)alkylene, mono- or            poly-carbonate(C₁-C₂₀)alkylene, polysilanylene,            polysiloxanylene and mixtures thereof, wherein the at least            one substituent is connected to an aryl group of a            photochromic material;        -   (iii) —CH(CN)₂ and —CH(COOX₁)₂, wherein X₁ is chosen from at            least one of a lengthening agent L, hydrogen, C₁-C₁₈ alkyl            that is unsubstituted or mono-substituted with phenyl,            phenyl(C₁-C₁₈)alkyl that is mono-substituted with C₁-C₁₈            alkyl, C₁-C₁₈ haloalkyl or C₁-C₁₈ alkoxy, and an aryl group            that is unsubstituted, mono- or di-substituted, wherein each            aryl substituent is independently chosen from C₁-C₁₈ alkyl            and C₁-C₁₈ alkoxy; and lengthening agent L;        -   (iv) —CH(X₂)(X₃), wherein:            -   (1) X₂ is chosen from at least one of a lengthening                agent L, hydrogen, C₁-C₁₈ alkyl, and an aryl group that                is unsubstituted, mono- or di-substituted, wherein each                aryl substituent is independently chosen from C₁-C₁₈                alkyl and C₁-C₁₈ alkoxy; and            -   (2) X₃ is chosen from at least one of —COOX₁, —COX₁,                —COX₄, and —CH₂OX₅, wherein: X₄ is chosen from at least                one of morpholino, piperidino, amino that is                unsubstituted, mono- or di-substituted with C₁-C₁₈                alkyl, and an unsubstituted, mono or di-substituted                group chosen from phenylamino and diphenylamino, wherein                each substituent is independently chosen from C₁-C₁₈                alkyl or C₁-C₁₈ alkoxy; and X₅ is chosen from a                lengthening agent L, hydrogen, —C(O)X₂, C₁-C₁₈ alkyl                that is unsubstituted or mono-substituted with                (C₁-C₁₈)alkoxy or phenyl, phenyl(C₁-C₁₈)alkyl that is                mono-substituted with (C₁-C₁₈)alkoxy, and an aryl group                that is unsubstituted, mono- or di-substituted, wherein                each aryl substituent is independently chosen from                C₁-C₁₈ alkyl and C₁-C₁₈ alkoxy;        -   (v) an unsubstituted, mono-, di-, or tri-substituted aryl            group; 9-julolidinyl; or an unsubstituted, mono- or            di-substituted heteroaromatic group chosen from pyridyl,            furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl,            benzothien-2-yl, benzothien-3-yl, dibenzofuranyl,            dibenzothienyl, carbazoyl, benzopyridyl, Indolinyl, or            fluorenyl; wherein each aryl and heteroaromatic group            substituent is independently chosen for each occurrence            from:            -   (1) a lengthening agent L;            -   (2) —COOX₁ or —C(O)X₆;            -   (3) aryl, haloaryl, C₃-C₁₀ cycloalkylaryl, and an aryl                group that is mono- or di-substituted with C₁-C₁₈ alkyl                or C₁-C₁₈ alkoxy;            -   (4) C₁-C₁₈ alkyl, C₃-C₁₀ cycloalkyl, C₃-C₁₀                cycloalkyloxy(C₁-C₁₈)alkyl, aryl(C₁-C₁₈)alkyl,                aryloxy(C₁-C₁₈)alkyl, mono- or                di-(C₁-C₁₈)alkylaryl(C₁-C₁₈)alkyl, mono- or                di-(C₁-C₁₈)alkoxyaryl(C₁-C₁₈)alkyl, C₁-C₁₈ haloalkyl,                and mono(C₁-C₁₈)alkoxy(C₁-C₁₈)alkyl;            -   (5) C₁-C₁₈ alkoxy, C₃-C₁₀ cycloalkoxy,                cycloalkyloxy(C₁-C₁₈)alkoxy, aryl(C₁-C₁₈)alkoxy,                aryloxy(C₁-C₁₈)alkoxy, mono- or                di-(C₁-C₁₈)alkylaryl(C₁-C₁₈)alkoxy, and mono- or                di-(C₁-C₁₈)alkoxyaryl(C₁-C₁₈)alkoxy;            -   (6) aminocarbonyl, aminocarbonyl(C₁-C₁₈)alkylene, amino,                mono- or di-alkylamino, diarylamino, piperazino,                N—(C₁-C₁₈)alkylpiperazino, N-arylpiperazino, aziridino,                indolino, piperidino, morpholino, thiomorpholino,                tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidyl,                hydroxy, acryloxy, methacryloxy, and halogen;            -   (7) —OX₇ or —N(X₇)₂;            -   (8) —SX₁₁;            -   (9) a nitrogen containing ring represented by Formula i;            -   (10) a group represented by Formula ii or iii;            -   (11) an unsubstituted or mono-substituted group chosen                from pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl,                pyrrolidinyl, phenothiazinyl, phenoxazinyl, phenazinyl,                or acridinyl, wherein each substituent is independently                chosen from a lengthening agent L, C₁-C₁₈ alkyl, C₁-C₁₈                alkoxy, phenyl, hydroxy, amino or halogen;            -   (12) a group represented by Formula iv or v:

-   -   -   -   wherein:            -   (I) V is independently chosen in each formula from —O—,                —CH—, C₁-C₆ alkylene, and C₃-C₁₀ cycloalkylene,            -   (II) V is independently chosen in each formula from —O—                or —N(X₂₁)—, wherein X₂₁ is a lengthening agent L,                hydrogen, C₁-C₁₈ alkyl, and C₂-C₁₈ acyl, provided that                if V is —N(X₂₁)—, V is —CH₂—,            -   (III) X₁₈ and X₁₉ are each independently chosen from a                lengthening agent L, hydrogen and C₁-C₁₈ alkyl, and            -   (IV) k is chosen from 0, 1, and 2, and each X₂₀ is                independently chosen for each occurrence from a                lengthening agent L, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy,                hydroxy and halogen;            -   (13) a group represented by Formula vi:

-   -   wherein        -   (I) X₂₂ is chosen from a lengthening agent L, hydrogen and            C₁-C₁₈ alkyl, and        -   (II) X₂₃ is chosen from a lengthening agent L and an            unsubstituted, mono-, or di-substituted group chosen from            naphthyl, phenyl, furanyl and thienyl, wherein each            substituent is independently chosen for each occurrence from            C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, and halogen; and            -   (14) B and B′ together form fluoren-9-ylidene, mono- or                di-substituted fluoren-9-ylidene, or a saturated C₃-C₁₂                spiro-monocyclic hydrocarbon ring, e.g.,                cyclopropylidene, cyclobutylidene, cyclopentylidene,                cyclohexylidene, cycloheptylidene, cyclooctylidene,                cyclononylidene, cyclodecylidene cycloundecylidene,                cyclododecylidene; saturated C₇-C₁₂ spiro-bicyclic                hydrocarbon rings, e.g., bicyclo[2.2.1]heptylidene,                i.e., norbornylidene, 1,7,7-trimethyl                bicyclo[2.2.1]heptylidene, i.e., bornylidene,                bicyclo[3.2.1]octylidene, bicyclo[3.3.1]nonan-9-ylidene,                bicyclo[4.3.2]undecane; saturated C₇-C₁₂ spiro-tricyclic                hydrocarbon rings, e.g.,                tricyclo[2.2.1.0^(2,6)]heptylidene,                tricyclo[3.3.1.1^(3,7)]decylidene, i.e., adamantylidene,                and tricyclo[5.3.1.1^(2,6)]dodecyliden; and a                lengthening agent L, said fluoren-9-ylidene substituents                being selected from the group consisting of C₁-C₄ alkyl,                C₁-C₄ alkoxy, bromo, fluoro and chloro;        -   (D) provided that when said photochromic material is            represented by graphic formula II, Q comprises —N₃ or            —OCOOR′ provided that said photochromic material of graphic            formula II is substantially free of substituents at the            5-position; and R, i, B and B′ are the same as stated            hereinbefore;        -   (E) provided that when said photochromic material is            represented by graphic formula III, Q independently            comprises for each occurrence, —N₃ or —OCOOR′; and R, i, B            and B′ are the same as hereinbefore;        -   (F) provided that when said photochromic material is            represented by graphic formula IVA or IVB, Q independently            comprises for each occurrence-N₃; or —CCR′, provided that            the indolino group is substantially free of N-substituents;            or —OSO₂R′″, provided that said photochromic material is            substantially free of carbonyl groups and each R″ is            independently chosen for each occurrence from hydrogen, a            substituted or unsubstituted alkyl, cycloalkyl, arylalkyl,            or together form cycloalkyl that is substituted or            unsubstituted; and R and i are the same as hereinbefore;        -   (G) provided that when said photochromic material is            represented by graphic formula V, Q comprises —N₃, —CN,            —CCR′, or —OSO₂R′″; and R, i, B and B′ are the same as            hereinbefore; and        -   (H) provided that when said photochromic material is            represented by graphic formula VI, Q comprises: —N₃, —CN,            —CCR′, or —OSO₂R′″; E is —O— or —N(Q)-; and D is represented            by the following graphic formula:

-   -   -    wherein: T is —S—, —O— or —N(R)—, J is a spiro-alicyclic            ring and Q is the same as described hereinbefore.

According to one specific, non-limiting embodiment, wherein thephotochromic group comprises at least two PCs, the PCs can be linked toone another via linking group substituents on the individual PCs. Forexample, the PCs can be polymerizable photochromic groups orphotochromic groups that are adapted to be compatible with a hostmaterial (“compatibilized photochromic group”). Non-limiting examples ofpolymerizable photochromic groups from which PC can be chosen and thatare useful in conjunction with various non-limiting embodimentsdisclosed herein are disclosed in U.S. Pat. No. 6,113,814, which ishereby specifically incorporated by reference herein. Non-limitingexamples of compatibilized photochromic groups from which PC can bechosen and that are useful in conjunction with various non-limitingembodiments disclosed herein are disclosed in U.S. Pat. No. 6,555,028,which is hereby specifically incorporated by reference herein.

Other suitable photochromic groups and complementary photochromic groupsare described in U.S. Pat. No. 6,080,338 at column 2, line 21 to column14, line 43; U.S. Pat. No. 6,136,968 at column 2, line 43 to column 20,line 67; U.S. Pat. No. 6,296,785 at column 2, line 47 to column 31, line5; U.S. Pat. No. 6,348,604 at column 3, line 26 to column 17, line 15;U.S. Pat. No. 6,353,102 at column 1, line 62 to column 11, line 64; andU.S. Pat. No. 6,630,597 at column 2, line 16 to column 16, line 23; thedisclosures of the aforementioned patents are incorporated herein byreference.

Another non-limiting embodiment provides the aforementioned lengtheningagent (L) attached to the at least one photochromic group, wherein theat least one lengthening agent is chosen from one of the followingcompounds listed (and graphically represented) below:

Another non-limiting embodiment disclosed herein provides a photochromiccompound of graphic formula I represented by the following graphicformula:

Additionally, according to various non-limiting embodiments disclosedherein, the photochromic compound represented by Formulas I, II, III,IVA, IVB, V and VI may comprise one or more lengthening agents (L). Aspreviously discussed, in L, c, d, e, and f each can be independentlychosen from an integer ranging from 1 to 20, inclusive; and d′, e′ andf′ each can be independently chosen from 0, 1, 2, 3, and 4, providedthat the sum of d′+e′+f′ is at least 1. According to other non-limitingembodiments disclosed herein, c, d, e, and f each can be independentlychosen from an integer ranging from 0 to 20, inclusive; and d′, e′ andf′ each can be independently chosen from 0, 1, 2, 3, and 4, providedthat the sum of d′+e′+f′ is at least 2. According to still othernon-limiting embodiments disclosed herein, c, d, e, and f each can beindependently chosen from an integer ranging from 0 to 20, inclusive;and d′, e′ and f′ each can be independently chosen from 0, 1, 2, 3, and4, provided that the sum of d′+e′+f′ is at least 3. According to stillother non-limiting embodiments disclosed herein, c, d, e, and f each canbe independently chosen from an integer ranging from 0 to 20, inclusive;and d′, e′ and f′ each can be independently chosen from 0, 1, 2, 3, and4, provided that the sum of d′+e′+f′ is at least 1.

Thus, for example, in Formulas I, II, III, IVA, IVB, V and VI, “i” canbe at least 1 and at least one of the R groups can be a lengtheningagent L. Additionally or alternatively, the photochromic compound cancomprise at least one R group, at least one B group, or at least one B′group that is substituted with a lengthening agent L. For example,although not limiting herein, in one non-limiting embodiment thephotochromic compound can comprise a B group comprising a phenyl groupthat is mono-substituted with a lengthening agent L.

Moreover, although not limiting herein, according to variousnon-limiting embodiments disclosed herein, the lengthening agent (L) canbe attached to a photochromic group (e.g., the pyran group of Formula I,II, III or V) at any available position such that L extends or lengthensthe photochromic group in an activated state such that the absorptionratio of the extended photochromic group (i.e., the photochromiccompound) is enhanced as compared to the unextended photochromic group.Thus, for example and without limitation, according to variousnon-limiting embodiments wherein the photochromic compound isrepresented by Formula I, II, III or V, L can be directly bonded to thepyran group, for example, wherein i is at least 1 and R is L, or it canbe indirectly bonded to the pyran group, for example, as a substituenton an R group, B, or B′ group such that L extends the pyran group in anactivated state such that the absorption ratio of the photochromiccompound is enhanced as compared to the unextended pyran group.

Further, the photochromic compound according to various non-limitingembodiments disclosed herein and generally represented by Formula I, II,III, V and VI can have an average absorption ratio of at least 1.5 in anactivated state as determined according to CELL METHOD. According toother non-limiting embodiments, the photochromic compound can have anaverage absorption ratio ranging from 4 to 20, 3 to 30, or 2.5 to 50 inan activated state as determined according to CELL METHOD. According tostill other non-limiting embodiments, the photochromic compounds canhave an average absorption ratio ranging from 1.5 to 50 in an activatedstate as determined according to CELL METHOD.

Reaction sequences for forming a photochromic compound according tovarious non-limiting embodiments disclosed herein having an L group aredisclosed in Reaction Sequences A through J, K, M, N, P, Q, T in U.S.Pat. No. 7,342,112, which disclosure is incorporated herein byreference.

A general reaction scheme for preparing photochromic compoundsrepresented by Formulas I, II, III, IVA, IVB, V and VI, is shown in FIG.2. Starting with a photochromic compound having a hydroxyl group shownby Structure #1, or a photochromic compound of Structure #2 havingtriflate, as shown, or a halogen at the same position, photochromiccompounds of Structures #3, 5, 6, 7, 8, 9, 10 and 11 having Q groups of—OSO₂R′″, —CN, —COOR′, —OCOR′, —OCOOR′, —CCR′, —C(R′)C(R′)R′ and—CON(R′)R′, respectively, can be prepared. Examples 1, 2, 3 and 5 wereprepared following the general reaction scheme of FIG. 2.

The following abbreviations were used for the chemicals listed in thereaction schemes and examples described hereinafter:

-   -   DHP—3,4-dihydro-2H-pyran    -   DCC—dicyclohexylcarbodiimide    -   DMAP—4-dimethylaminopyridine    -   PPTS—pyridine p-toluenesulfonate    -   pTSA—p-toluenesulfonic acid    -   NMP—N-methyl pyrrolidone    -   THF—tetrahyrdofuran    -   KMnO₄—potassium permanganate    -   MeLi—methyl lithium    -   ppTs—pyridinium p-toluenesulfonate    -   (Tf)₂O—trifluoromethanesulfonic acid anhydride    -   Dppf—1,1′-bis(diphenylphosphino)ferrocene    -   Pd₂(dba)₃—tris(dibenzylideneacetone)dipalladium(0)    -   DIBAL—diisobutylaluminium hydride    -   t-BuOH—t-butanol    -   HOAc—acetic acid    -   PdCl₂(PPh₃)₂—bis(triphenylphosphine)paladium(II) chloride    -   CuI—copper iodide    -   PPhs—triphenyl phosphine    -   (iPr)₂NH: diisopropyl amine    -   EtMgBr—ethyl magnesium bromide    -   Zn(OAc)₂—zinc acetate    -   Zn(CN)₂—Zinc cyanide

Another general reaction scheme for making Q-substituted naphthols andQ-substituted phenol intermediates for preparing photochromic compoundsrepresented by Formulas I, II, III, IVA, IVB, and V, is shown in FIGS. 3and 4. Starting with a naphthol or phenol of Structure #12 in FIG. 3,one example of which can be prepared following Steps 1-3 of Example 4,naphthols of Structures #13, 14, 15, 19 and 21 having Q groups of —N₃,—CCR′, —CR′C(R′)R′, —COOR′, —CON(R′)R′, respectively, can be prepared.Starting with a naphthol or phenol of Structure #12 in FIG. 4, naphtholsof Structures #22, 24, 28, 29 and 30 having Q groups of —CN, —SR′,—OSO₂R′″, —OCOOR′, and —OCOR′, respectively, can be prepared. TheQ-substituted naphthols and Q-substituted phenol intermediates preparedin the reaction schemes of FIGS. 3 and 4 can be used in a couplingreaction with appropriate propargyl alcohols, as known to those skilledin the art, and described for benzopyrans in Reaction C of U.S. Pat. No.5,429,774 and for naphthopyrans in Reaction E of U.S. Pat. No. 5,458,814and for indenonaphthopyrans in Reaction G of U.S. Pat. No. 7,262,295,the disclosures of these reactions are incorporated herein by reference.Examples 4, 6 and 7 were prepared following the general reaction schemesof FIGS. 3 and 4.

Another non-limiting embodiment provides a photochromic compound chosenfrom:

-   (a)    3-phenyl-3-(4-(4-methoxyphenylpiperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-trifluoromethanesulfonyloxy-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (b)    3-phenyl-3-(4-(4-methoxyphenylpiperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-cyano-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (c)    3-phenyl-3-(4(4-methoxyphenylpiperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(2-hydroxy-2-methyl-3-butyn-4-yl)-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;-   (d)    2-phenyl-2-[4-(4-methoxy-phenyl)-piperazin-1-yl]-phenyl-5-methoxycarbonyl-6-methyl-8-cyano-2H-naphtho[1,2-b]pyran;-   (e)    2,2-bis(4-methoxyphenyl)-5-methoxyethylcarbonyl-6-methyl-8-vinyl-2H-naphtho[1,2-b]pyran;-   (f)    2,2-bis(4-methoxyphenyl)-5-methoxyethoxycarbonyl-6-methyl-8-hydroxycarbonyl-2H-naphtho[1,2-b]pyran;    and-   (g)    2,2-bis(4-methoxyphenyl)-5-methoxyethylcarbonyl-6-methyl-8-methoxycarbonyl-2H-naphtho-[1,2-b]pyran.

Also provided by the present invention is a naphthol represented by oneof the following graphic formulae:

wherein:

-   -   (A) each substituent Q independently comprising —N₃, —CN,        —COOR′, —CCR′, —C(R′)C(R′)R′, —OCOR′, —OCOOR′, —SR′, —OSO₂R′″,        and/or —CON(R′)R′, wherein each R′ independently comprises        hydrogen, an unsubstituted or substituted alkyl group having        from 1 to 18 carbon atoms, an unsubstituted or substituted aryl        group, an unsubstituted or substituted alkene or alkyne group        having from 2 to 18 carbon atoms, wherein said substituents are        chosen from halo and hydroxyl and R′″ comprises —CF₃ or a        perfluorinated alkyl group having from 2 to 18 carbon atoms;    -   (B) each i is an integer chosen from 0 to the total number of        available positions and each R is independently chosen for each        occurrence from:        -   (a) hydrogen, C₁-C₁₈ alkyl, C₂-C₁₈ alkylidene, C₂-C₁₈            alkylidyne, vinyl, C₃-C₁₀ cycloalkyl, C₁-C₁₈ haloalkyl,            allyl, halogen, and benzyl that is unsubstituted or            mono-substituted with at least one of C₁-C₁₈ alkyl and            C₁-C₁₈ alkoxy;        -   (b) phenyl that is mono-substituted at the para position            with at least one substituent chosen from: C₁-C₁₈ alkoxy,            linear or branched chain C₁-C₂₀ alkylene, linear or branched            chain C₁-C₁₈ polyoxyalkylene, cyclic C₃-C₂₀ alkylene,            phenylene, naphthylene, C₁-C₁₈ alkyl substituted phenylene,            mono- or poly-urethane(C₁-C₂₀)alkylene, mono- or            poly-ester(C₁-C₂₀)alkylene, mono- or            poly-carbonate(C₁-C₂₀)alkylene, polysilanylene,            polysiloxanylene and mixtures thereof, wherein the at least            one substituent is connected to an aryl group of a            photochromic material;        -   (c) —CH(CN)₂ and —CH(COOX₁)₂, wherein X₁ is chosen from at            least one of a lengthening agent L, hydrogen, C₁-C₁₈ alkyl            that is unsubstituted or mono-substituted with phenyl,            phenyl(C₁-C₁₈)alkyl that is mono-substituted with C₁-C₁₈            alkyl, C₁-C₁₈ haloalkyl, or C₁-C₁₈ alkoxy, and an aryl group            that is unsubstituted, mono- or di-substituted, wherein each            aryl substituent is independently chosen from C₁-C₁₈ alkyl,            C₁-C₁₈ haloalkyl, lengthening agent L and C₁-C₁₈ alkoxy;        -   (d) —CH(X₂)(X₃), wherein:            -   (i) X₂ is chosen from at least one of a lengthening                agent L, hydrogen, C₁-C₁₈ alkyl, and an aryl group that                is unsubstituted, mono- or di-substituted, wherein each                aryl substituent is independently chosen from C₁-C₁₈                alkyl and C₁-C₁₈ alkoxy; and            -   (ii) X₃ is chosen from at least one of —COOX₁, —COX₁,                —COX₄, and —CH₂OX₅, wherein:    -   (A) X₄ is chosen from at least one of morpholino, piperidino,        amino that is unsubstituted, mono- or di-substituted with C₁-C₁₈        alkyl, and an unsubstituted, mono or di-substituted group chosen        from phenylamino and diphenylamino, wherein each substituent is        independently chosen from C₁-C₁₈ alkyl or C₁-C₁₈ alkoxy; and    -   (B) X₅ is chosen from a lengthening agent L, hydrogen, —C(O)X₂,        C₁-C₁₈ alkyl that is unsubstituted or mono-substituted with        (C₁-C₁₈)alkoxy or phenyl, phenyl(C₁-C₁₈)alkyl that is        mono-substituted with (C₁-C₁₈)alkoxy, and an aryl group that is        unsubstituted, mono- or di-substituted, wherein each aryl        substituent is independently chosen from C₁-C₁₈ alkyl and C₁-C₁₈        alkoxy;        -   (e) an unsubstituted, mono-, di-, or tri-substituted aryl            group; 9-julolidinyl; or an unsubstituted, mono- or            di-substituted heteroaromatic group chosen from pyridyl,            furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl,            benzothien-2-yl, benzothien-3-yl, dibenzofuranyl,            dibenzothienyl, carbazoyl, benzopyridyl, indolinyl, and            fluorenyl; wherein each aryl and heteroaromatic substituent            is independently chosen for each occurrence from:            -   (i) a lengthening agent L;            -   (ii) —COOX₁ or —C(O)X₆, wherein X₆ is chosen from at                least one of: a lengthening agent L, hydrogen, C₁-C₁₈                alkoxy, phenoxy that is unsubstituted, mono- or                di-substituted with C₁-C₁₈ alkyl or C₁-C₁₈ alkoxy, an                aryl group that is unsubstituted, mono- or                di-substituted with C₁-C₁₈ alkyl or C₁-C₁₈ alkoxy, an                amino group that is unsubstituted, mono- or                di-substituted with C₁-C₁₈ alkyl, and a phenylamino                group that is unsubstituted, mono- or di-substituted                with C₁-C₁₈ alkyl or C₁-C₁₈ alkoxy;            -   (iii) aryl, haloaryl, C₃-C₁₀ cycloalkylaryl, and an aryl                group that is mono- or di-substituted with C₁-C₁₈ alkyl                or C₁-C₁₈ alkoxy;            -   (iv) C₁-C₁₈ alkyl, C₃-C₁₀ cycloalkyl, C₃-C₁₀                cycloalkyloxy(C₁-C₁₈)alkyl, aryl(C₁-C₁₈)alkyl,                aryloxy(C₁-C₁₈)alkyl, mono- or                di-(C₁-C₁₈)alkylaryl(C₁-C₁₈)alkyl, mono- or                di-(C₁-C₁₈)alkoxyaryl(C₁-C₁₈)alkyl, C₁-C₁₈ haloalkyl,                and mono(C₁-C₁₈)alkoxy(C₁-C₁₈)alkyl;            -   (v) C₁-C₁₈ alkoxy, C₃-C₁₀ cycloalkoxy;                cycloalkyloxy(C₁-C₁₈)alkoxy, aryl(C₁-C₁₈)alkoxy,                aryloxy(C₁-C₁₈)alkoxy, mono- or                di-(C₁-C₁₈)alkylaryl(C₁-C₁₈)alkoxy, and mono- or                di-(C₁-C₁₈)alkoxyaryl(C₁-C₁₈)alkoxy;            -   (vi) aminocarbonyl, aminocarbonyl(C₁-C₁₈)alkylene,                amino, mono- or di-(C₁-C₁₈)alkylamino, diarylamino,                piperazino, N—(C₁-C₁₈)alkylpiperazino, N-arylpiperazino,                aziridino, indolino, piperidino, morpholino,                thiomorpholino, tetrahydroquinolino,                tetrahydroisoquinolino, pyrrolidyl, hydroxy, acryloxy,                methacryloxy, and halogen;            -   (vii) —OX₇ or —N(X₇)₂, wherein X₇ is chosen from:    -   (A) a lengthening agent L, hydrogen, C₁-C₁₈ alkyl, C₁-C₁₈ alkyl,        phenyl(C₁-C₁₈)alkyl, mono(C₁-C₁₈)alkyl substituted        phenyl(C₁-C₁₈)alkyl, mono(C₁-C₁₈)alkoxy substituted        phenyl(C₁-C₁₈)alkyl; C₁-C₁₈ alkoxy(C₁-C₁₈)alkyl; C₃-C₁₀        cycloalkyl; mono(C₁-C₁₈)alkyl substituted C₃-C₁₀ cycloalkyl,        C₁-C₁₈ haloalkyl, allyl, benzoyl, mono-substituted benzoyl,        naphthoyl or mono-substituted naphthoyl, wherein each of said        benzoyl and naphthoyl substituents are independently chosen from        C₁-C₁₈ alkyl, and C₁-C₁₈ alkoxy;    -   (B) —CH(X₈)X₉, wherein X₈ is chosen from a lengthening agent L,        hydrogen or C₁-C₁₈ alkyl; and X₉ is chosen from a lengthening        agent L, —CN, —CF₃, or —COOX₁₀, wherein X₁₀ is chosen from a        lengthening agent L, hydrogen or C₁-C₁₈ alkyl;    -   (C) —C(O)X₆; or    -   (D) tri(C₁-C₁₈)alkylsilyl, tri(C₁-C₁₈)alkylsilyloxy,        tri(C₁-C₁₈)alkoxysilyl, tri(C₁-C₁₈)alkoxysilyloxy,        di(C₁-C₁₈)alkyl(C₁-C₁₈ alkoxy)silyl, di(C₁-C₁₈)alkyl(C₁-C₁₈        alkoxy)silyloxy, di(C₁-C₁₈)alkoxy(C₁-C₁₈ alkyl)silyl or        di(C₁-C₁₈)alkoxy(C₁-C₁₈ alkyl)silyloxy;        -   (viii) SX₁₁, wherein X₁₁ is chosen from a lengthening agent            L, hydrogen, C₁-C₁₈ alkyl, C₁-C₁₈ haloalkyl, an aryl group            that is unsubstituted, or mono- or di-substituted with            C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, or halogen;        -   (ix) a nitrogen containing ring represented by Formula i:

-   -   -   -   wherein

    -   (A) n is an integer chosen from 0, 1, 2, and 3, provided that if        n is 0, U′ is U, and each U is independently chosen for each        occurrence from —CH₂—, —CH(X₁₂)—, —C(X₁₂)₂—, —CH(X₁₃)—,        —C(X₁₃)₂—, and —C(X₁₂)(X₁₃)—, wherein X₁₂ is chosen from a        lengthening agent L and C₁-C₁₈ alkyl, and X₁₃ is chosen from a        lengthening agent L, phenyl and naphthyl, and

    -   (B) U′ is chosen from U, —O—, —S—, —S(O)—, —NH—, —N(X₁₂)— or        —N(X₁₃)—, and m is an integer chosen from 1, 2, and 3, and        -   (x) a group represented by Formula ii or iii:

-   -   wherein X₁₄, X₁₅, and X₁₆ are independently chosen for each        occurrence from a lengthening agent L, hydrogen, C₁-C₁₈ alkyl,        phenyl or naphthyl, or X₁₄ and X₁₅ together form a ring of 5 to        8 carbon atoms; p is an integer chosen from 0, 1, or 2, and X₁₇        is independently chosen for each occurrence from a lengthening        agent L, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, or halogen;        -   (f) an unsubstituted or mono-substituted group chosen from            pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl,            pyrrolidinyl, phenothiazinyl, phenoxazinyl, phenazinyl, or            acridinyl, wherein each substituent is independently chosen            from a lengthening agent L, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy,            phenyl, hydroxy, amino or halogen;        -   (g) a group represented by Formula iv or v:

-   -   wherein        -   (i) V is independently chosen in each formula from —O—,            —CH—, C₁-C₆ alkylene, and C₃-C₁₀ cycloalkylene,        -   (ii) V is independently chosen in each formula from —O— or            —N(X₂₁)—, wherein X₂₁ is from a lengthening agent L            represented by Formula I above, hydrogen, C₁-C₁₈ alkyl, and            C₂-C₁₈ acyl, provided that if V is —N(X₂₁)—, V′ is —CH—,        -   (iii) X₁₈ and X₁₉ are each independently chosen from a            lengthening agent L, hydrogen and C₁-C₁₈ alkyl, and        -   (iv) k is chosen from 0, 1, and 2, and each X₂₀ is            independently chosen for each occurrence from a lengthening            agent L, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, hydroxy and halogen;    -   (h) a group represented by Formula vi:

-   -   -   (i) X₂₂ is chosen from a lengthening agent L, hydrogen and            C₁-C₁₈ alkyl, and        -   (ii) X₂₃ is chosen from a lengthening agent L and an            unsubstituted, mono-, or di-substituted group chosen from            aryl, furanyl and thienyl, wherein each substituent is            independently chosen for each occurrence from C₁-C₁₈ alkyl,            C₁-C₁₈ alkoxy, and halogen;        -   (i) —C(O)X₂₄, wherein X₂₄ is chosen from a lengthening agent            L, hydroxy, C₁-C₁₈ alkyl, C₁-C₁₈ haloalkyl, C₁-C₁₈ alkoxy,            phenyl that is unsubstituted or mono-substituted with C₁-C₁₈            alkyl or C₁-C₁₈ alkoxy, amino that is unsubstituted, mono-            or di-substituted with at least one of C₁-C₁₈ alkyl, aryl            and benzyl;

    -   (j) —COOX₁;

    -   (k) —OX₇ and —N(X₇)₂;        -   (l) —SX₁₁;        -   (m) the nitrogen containing ring represented by Formula i;        -   (n) the group represented by one of Formula ii or iii;        -   (o) a lengthening agent L represented by:

[S₁]_(c)-[Q₁-[S₂]_(d)]_(d′)-[Q₂-[S₃]_(e)]_(e′)[Q₃-[S₄]_(f)]_(f′)—S₅—Pwherein:

-   -   -   -   (i) each Q₁, Q₂, and Q₃ is independently chosen for each                occurrence from: a divalent group chosen from: an                unsubstituted or a substituted aromatic group, an                unsubstituted or a substituted alicyclic group, an                unsubstituted or a substituted heterocyclic group, and                mixtures thereof, wherein substituents are chosen from:                a group represented by P, liquid crystal mesogens,                halogen, poly(C₁-C₁₈ alkoxy), C₁-C₁₈ alkoxycarbonyl,                C₁-C₁₈ alkylcarbonyl, C₁-C₁₈ alkoxycarbonyloxy,                aryloxycarbonyloxy, perfluoro(C₁-C₁₈)alkoxy,                perfluoro(C₁-C₁₈)alkoxycarbonyl,                perfluoro(C₁-C₁₈)alkylcarbonyl,                perfluoro(C₁-C₁₈)alkylamino,                di-(perfluoro(C₁-C₁₈)alkyl)amino,                perfluoro(C₁-C₁₈)alkylthio, C₁-C₁₈ alkylthio, C₁-C₁₈                acetyl, C₃-C₁₀ cycloalkyl, C₃-C₁₀ cycloalkoxy, a                straight-chain or branched C₁-C₁₈ alkyl group that is                mono-substituted with cyano, halo, or C₁-C₁₈ alkoxy, or                poly-substituted with halo, and a group comprising one                of the following formulae: -M(T)_((t-1)) and                -M(OT)_((t-1)), wherein M is chosen from aluminum,                antimony, tantalum, titanium, zirconium and silicon, T                is chosen from organofunctional radicals,                organofunctional hydrocarbon radicals, aliphatic                hydrocarbon radicals and aromatic hydrocarbon radicals,                and t is the valence of M;            -   (ii) c, d, e, and f are each independently chosen from                an integer ranging from 0 to 20, inclusive; and each S₁,                S₂, S₃, S₄, and S₅ is independently chosen for each                occurrence from a spacer unit chosen from:                -   (1) —(CH₂)_(g), —(CF₂)_(h)—, —Si(CH₂)_(g),                    —(Si[(CH₃)₂]O)_(h)—, wherein g is independently                    chosen for each occurrence from 1 to 20; h is a                    whole number from 1 to 16 inclusive;                -   (2) —N(Z)—, —C(Z)═C(Z)—, —C(Z)═N—, —C(Z)—C(Z′)— or a                    single bond, wherein Z is independently chosen for                    each occurrence from hydrogen, C₁-C₁₈ alkyl, C₃-C₁₀                    cycloalkyl and aryl, and Z′ is independently chosen                    for each occurrence from C₁-C₁₈ alkyl, C₃-C₁₀                    cycloalkyl and aryl; and                -   (3) —O—, —C(O)—, —C≡C—, —N═N—, —S—, —S(O)—,                    —S(O)(O)—, —(O)S(O)—, —(O)S(O)O—, —O(O)S(O)O—, or                    straight-chain or branched C₁-C₂₄ alkylene residue,                    said C₁-C₂₄ alkylene residue being unsubstituted,                    mono-substituted by cyano or halo, or                    poly-substituted by halo; provided that when two                    spacer units comprising heteroatoms are linked                    together the spacer units are linked so that                    heteroatoms are not directly linked to each other                    and when S₁ and S₅ are linked to PC and P,                    respectively, they are linked so that two                    heteroatoms are not directly linked to each other;            -   (iii) P is chosen from: hydroxy, amino, C₂-C₁₈ alkenyl,                C₂-C₁₈ alkynyl, azido, silyl, siloxy, silylhydride,                (tetrahydro-2H-pyran-2-yl)oxy, thio, isocyanato,                thioisocyanato, acryloyloxy, methacryloyloxy,                2-(acryloyloxy)ethylcarbamyl,                2-(methacryloyloxy)ethylcarbamyl, aziridinyl,                allyloxycarbonyloxy, epoxy, carboxylic acid, carboxylic                ester, acryloylamino, methacryloylamino, aminocarbonyl,                C₁-C₁₈ alkyl aminocarbonyl, aminocarbonyl(C₁-C₁₈)alkyl,                C₁-C₁₈ alkyloxycarbonyloxy, halocarbonyl, hydrogen,                aryl, hydroxy(C₁-C₁₈)alkyl, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy,                amino(C₁-C₁₈)alkyl, C₁-C₁₈ alkylamino,                di-(C₁-C₁₈)alkylamino, C₁-C₁₈ alkyl(C₁-C₁₈)alkoxy,                C₁-C₁₈ alkoxy(C₁-C₁₈)alkoxy, nitro, poly(C₁-C₁₈)alkyl                ether, (C₁-C₁₈)alkyl(C₁-C₁₈)alkoxy(C₁-C₁₈)alkyl,                polyethyleneoxy, polypropyleneoxy, ethylenyl, acryloyl,                acryloyloxy(C₁-C₁₈)alkylene, methacryloyl,                methacryloyloxy(C₁-C₁₈)alkyl, 2-chloroacryloyl,                2-phenylacryloyl, acryloyloxyphenyl,                2-chloroacryloylamino, 2-phenylacryloylamino-carbonyl,                oxetanyl, glycidyl, cyano, isocyanato(C₁-C₁₈)alkyl,                itaconic acid ester, vinyl ether, vinyl ester, a styrene                derivative, main-chain and side-chain liquid crystal                polymers, siloxane derivatives, ethyleneimine                derivatives, maleic acid derivatives, fumaric acid                derivatives, unsubstituted cinnamic acid derivatives,                cinnamic acid derivatives that are substituted with at                least one of methyl, methoxy, cyano and halogen, or                substituted or unsubstituted chiral or non-chiral                monovalent or divalent groups chosen from steroid                radicals, terpenoid radicals, alkaloid radicals and                mixtures thereof, wherein the substituents are                independently chosen from C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy,                amino, C₃-C₁₀ cycloalkyl, C₁-C₁₈ alkyl(C₁-C₁₈)alkoxy,                fluoro(C₁-C₁₈)alkyl, cyano, cyano(C₁-C₁₈)alkyl,                cyano(C₁-C₁₈)alkoxy or mixtures thereof, or P is a                structure having from 2 to 4 reactive groups or P is an                unsubstituted or substituted ring opening metathesis                polymerization precursor; and            -   (iv) d′, e′ and f′ are each independently chosen from 0,                1, 2, 3, and 4, provided that a sum of d′+e′+f′ is at                least 1;

        -   (p) immediately adjacent R groups together form a group            represented by Formula vii, viii, or ix:

-   -   -   -   wherein                -   (i) W and W′ are independently chosen for each                    occurrence from —O—, —N(X₇)—, —C(X₁₄)—, —C(X₁₇)—,                -   (ii) X₁₄, X₁₆ and X₁₇ are as set forth above, and                -   (iii) q is an integer chosen from 0, 1, 2, 3, and 4;                    and

    -   (C) the group A represents indeno, thiopheno, benzothiopheno,        furo or benzofuro.

In particular embodiments of the present invention, the naphthol may berepresented by one of the following graphic formulae:

-   -   wherein each substituent Q independently comprises —CN, —COOR′,        —CCR′, —C(R′)C(R′)R′, —OCOR′, —OCOOR′, —SR′, —OSO₂R′″, and/or        —CON(R′)R′, wherein each R′ independently comprises an alkyl        group having from 1 to 12 carbon atoms and R′″ comprises —CF₃ or        a perfluorinated alkyl group having from 2 to 12 carbon atoms        and the group A is indeno.

In another particular embodiment, the naphthol may be represented by thefollowing graphic formula:

Further reaction schemes for preparing the naphthols of the presentinvention are described in FIGS. 5 and 6. In both reaction schemes, agroup Q′ which can be converted into Q is used. Examples of Q′ includealkoxy and halogen groups. The conversion of Q′ into Q may occur at thenaphthol or photochromic compound stage. In Example 4, Q′ is convertedinto Q at the naphthol stage and in Example 1, Q′ is converted into Q atthe photochromic compound stage. FIG. 5 shows how substitutedindeno-fused naphthols are prepared. The synthesis sequence starts frombenzophenone of Structure #31, which has the desired substitutions (Q′and R′) in place. Such materials are commercially available or preparedby methods known to those skilled in the art. A Stobbe reaction ofStructure #31 with dimethyl succinate in the presence of potassiumt-butoxide provides condensed product of Structure #32, which easilyundergoes a ring closure reaction in acetic anhydride to form thenaphthol of Structure #33. The naphthol can be further converted toindeno-fused naphthol of Structure #34 with various substitutions on thebridge carbon via various multistep reactions that can be found in U.S.Pat. Nos. 5,645,767; 5,869,658; 5,698,141; 5,723,072; 5,961,892;6,113,814; 5,955,520; 6,555,028; 6,296,785; 6,555,028; 6,683,709;6,660,727; 6,736,998; 7,008,568; 7,166,357; 7,262,295; and 7,320,826,which patents are incorporated herein by reference.

FIG. 6 shows how Q′ substituted naphthols are prepared in a similarmanner as done in FIG. 5. Starting with the ketone of Structure #36, aStobbe reaction of Structure #35 with dimethyl succinate in the presenceof potassium t-butoxide provides condensed product of Structure #36,which easily undergoes a ring closure reaction in acetic anhydride toform the compound of Structure #37 which is further converted to thenaphthol of Structure #38. Naphthols having Q′ substituents at variouslocations can be prepared using procedures known to those skilled in theart.

The thermally reversible photochromic compounds according to variousnon-limiting embodiments disclosed herein can be used in a variety ofapplications to provide photochromic and/or photochromic-dichroicproperties.

One non-limiting embodiment provides a photochromic article comprisingan organic host material and a photochromic composition of the presentinvention connected to at least a portion of the organic host material.As used herein the term “connected to” means in direct contact with anobject or indirect contact with an object through one or more otherstructures or materials, at least one of which is in direct contact withthe object. Further, according to this non-limiting embodiment, thephotochromic compound can be connected to at least a portion of the hostby incorporation into the host material or by application onto the hostmaterial, for example, as part of a coating or layer. In addition to thephotochromic compound, the photochromic composition may further compriseat least one additive chosen from dyes, alignment promoters, kineticenhancing additives, photoinitiators, thermal initiators, polymerizationinhibitors, solvents, light stabilizers, heat stabilizers, mold releaseagents, rheology control agents, leveling agents, free radicalscavengers, gelators and adhesion promoters.

Non-limiting examples of organic host materials that may be used inconjunction with various non-limiting embodiments disclosed hereininclude polymeric materials, for example, homopolymers and copolymers,prepared from the monomers and mixtures of monomers disclosed in U.S.Pat. No. 5,962,617 and in U.S. Pat. No. 5,658,501 from column 15, line28 to column 16, line 17, the disclosures of which U.S. patents arespecifically incorporated herein by reference, an oligomeric material, amonomeric material or a mixture or combination thereof. Polymericmaterials can be thermoplastic or thermoset polymeric materials, can betransparent or optically clear, and can have any refractive indexrequired. Non-limiting examples of such disclosed monomers and polymersinclude: polyol(allyl carbonate) monomers, e.g., allyl diglycolcarbonates such as diethylene glycol bis(allyl carbonate), which monomeris sold under the trademark CR-39 by PPG Industries, Inc.;polyurea-polyurethane (polyurea-urethane) polymers, which are prepared,for example, by the reaction of a polyurethane prepolymer and a diaminecuring agent, a composition for one such polymer being sold under thetrademark TRIVEX by PPG Industries, Inc.; polyol(meth)acryloylterminated carbonate monomer; diethylene glycol dimethacrylate monomers;ethoxylated phenol methacrylate monomers; diisopropenyl benzenemonomers; ethoxylated trimethylol propane triacrylate monomers; ethyleneglycol bismethacrylate monomers; poly(ethylene glycol) bismethacrylatemonomers; urethane acrylate monomers; poly(ethoxylated bisphenol Adimethacrylate); poly(vinyl acetate); poly(vinyl alcohol); poly(vinylchloride); poly(vinylidene chloride); polyethylene; polypropylene;polyurethanes; polythiourethanes; thermoplastic polycarbonates, such asthe carbonate-linked resin derived from bisphenol A and phosgene, onesuch material being sold under the trademark LEXAN; polyesters, such asthe material sold under the trademark MYLAR; poly(ethyleneterephthalate); polyvinyl butyral; poly(methyl methacrylate), such asthe material sold under the trademark PLEXIGLAS, and polymers preparedby reacting polyfunctional isocyanates with polythiols or polyepisulfidemonomers, either homopolymerized or co- and/or terpolymerized withpolythiols, polyisocyanates, polyisothiocyanates and optionallyethylenicaly unsaturated monomers or halogenated aromatic-containingvinyl monomers. Also contemplated are copolymers of such monomers andblends of the described polymers and copolymers with other polymers, forexample, to form block copolymers or interpenetrating network products.

According to one specific non-limiting embodiment, the organic hostmaterial is chosen from polyacrylates, polymethacrylates, poly(C₁-C₁₂)alkyl methacrylates, polyoxy(alkylene methacrylates), poly (alkoxylatedphenol methacrylates), cellulose acetate, cellulose triacetate,cellulose acetate propionate, cellulose acetate butyrate, poly(vinylacetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidenechloride), poly(vinylpyrrolidone), poly((meth)acrylamide), poly(dimethylacrylamide), poly(hydroxyethyl methacrylate), poly((meth)acrylic acid),thermoplastic polycarbonates, polyesters, polyurethanes,polythiourethanes, poly(ethylene terephthalate), polystyrene, poly(alphamethylstyrene), copoly(styrene-methylmethacrylate),copoly(styrene-acrylonitrile), polyvinylbutyral and polymers of membersof the group consisting of polyol(allyl carbonate)monomers,mono-functional acrylate monomers, mono-functional methacrylatemonomers, polyfunctional acrylate monomers, polyfunctional methacrylatemonomers, diethylene glycol dimethacrylate monomers, diisopropenylbenzene monomers, alkoxylated polyhydric alcohol monomers anddiallylidene pentaerythritol monomers.

According to another specific non-limiting embodiment, the organic hostmaterial is a homopolymer or copolymer of monomer(s) chosen fromacrylates, methacrylates, methyl methacrylate, ethylene glycol bismethacrylate, ethoxylated bisphenol A dimethacrylate, vinyl acetate,vinylbutyral, urethane, thiourethane, diethylene glycol bis(allylcarbonate), diethylene glycol dimethacrylate, dilsopropenyl benzene, andethoxylated trimethylol propane triacrylate. The polymeric material mostoften comprises self-assembling materials, polycarbonate, polyamide,polyimide, poly(meth)acrylate, polycyclic alkene, polyurethane,poly(urea)urethane, polythiourethane, polythio(urea)urethane,polyol(allyl carbonate), cellulose acetate, cellulose diacetate,cellulose triacetate, cellulose acetate propionate, cellulose acetatebutyrate, polyalkene, polyalkylene-vinyl acetate, poly(vinylacetate),poly(vinyl alcohol), poly(vinyl chloride), poly(vinylformal),poly(vinylacetal), poly(vinylidene chloride), poly(ethyleneterephthalate), polyester, polysulfone, polyolefin, copolymers thereof,and/or mixtures thereof.

Further, according to various non-limiting embodiments disclosed herein,the organic host material can form an optical element or portionthereof. Non-limiting examples of optical elements include ophthalmicelements, display elements, windows, and mirrors. As used herein theterm “optical” means pertaining to or associated with light and/orvision. For example, although not limiting herein, according to variousnon-limiting embodiments, the optical element or device can be chosenfrom ophthalmic elements and devices, display elements and devices,windows, mirrors, packaging material, and active and passive liquidcrystal cell elements and devices.

As used herein the term “ophthalmic” means pertaining to or associatedwith the eye and vision. Non-limiting examples of ophthalmic elementsinclude corrective and non-corrective lenses, including single vision ormulti-vision lenses, which may be either segmented or non-segmentedmulti-vision lenses (such as, but not limited to, bifocal lenses,trifocal lenses and progressive lenses), as well as other elements usedto correct, protect, or enhance (cosmetically or otherwise) vision,including without limitation, contact lenses, intra-ocular lenses,magnifying lenses, and protective lenses or visors. As used herein theterm “display” means the visible or machine-readable representation ofinformation in words, numbers, symbols, designs or drawings.Non-limiting examples of display elements and devices include screens,monitors, and security elements, including without limitation, securitymarks and authentication marks. As used herein the term “window” meansan aperture adapted to permit the transmission of radiationtherethrough. Non-limiting examples of windows include automotive andaircraft transparencies, filters, shutters, and optical switches. Asused herein the term “mirror” means a surface that specularly reflects alarge fraction of incident light.

For example, in one non-limiting embodiment, the organic host materialis an ophthalmic element, and more particularly, is an ophthalmic lens.

Further, it is contemplated that the photochromic compounds disclosedherein can be used alone or in conjunction with at least one othercomplementary organic photochromic compound having at least oneactivated absorption maxima within the range of 300 nm to 1000 nm,inclusive (or substances containing the same). For example, thephotochromic compound disclosed herein can be combined with at least oneother conventional organic photochromic compound such that thecombination of photochromic compound, when activated, exhibits a desiredhue. Non-limiting examples of suitable conventional organic photochromiccompounds include those photochromic pyrans, oxazines, and fulgides, setforth above. Other complementary photochromic compounds include, forexample, the pyrans, oxazines, fulgides and fulgimides describedhereinafter.

Non-limiting examples of thermally reversible complementary photochromicpyrans include benzopyrans, naphthopyrans, e.g., naphtho[1,2-b]pyrans,naphtho[2,1-b]pyrans, indeno-fused naphthopyrans, such as thosedisclosed in U.S. Pat. No. 5,645,767, and heterocyclic-fusednaphthopyrans, such as those disclosed in U.S. Pat. Nos. 5,723,072,5,698,141, 6,153,126, and 6,022,497, which are hereby incorporated byreference; spiro-9-fluoreno[1,2-b]pyrans; phenanthropyrans; quinopyrans;fluoroanthenopyrans; spiropyrans, e.g.,spiro(benzindoline)naphthopyrans, spiro(indoline)benzopyrans,spiro(indoline)naphthopyrans, spiro(indoline)quinopyrans andspiro(indoline)pyrans. More specific examples of naphthopyrans and thecomplementary organic photochromic substances are described in U.S. Pat.No. 5,658,501, which are hereby specifically incorporated by referenceherein. Spiro(indoline)pyrans are also described in the text, Techniquesin Chemistry, Volume III, “Photochromism”, Chapter 3, Glenn H. Brown,Editor, John Wiley and Sons, Inc., New York, 1971, which is herebyincorporated by reference.

Non-limiting examples of thermally reversible complementary photochromicoxazines include benzoxazines, naphthoxazines, and spiro-oxazines, e.g.,spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines,spiro(benzindoline)pyridobenzoxazines,spiro(benzindoline)naphthoxazines, spiro(indoline)benzoxazines,spiro(indoline)fluoranthenoxazine, and spiro(indoline)quinoxazine.

More non-limiting examples of thermally reversible complementaryphotochromic fulgides include: fulgimides, and the 3-furyl and 3-thienylfulgides and fulgimides, which are disclosed in U.S. Pat. No. 4,931,220(which are hereby specifically incorporated by reference) and mixturesof any of the aforementioned photochromic materials/compounds.

For example, it is contemplated that the photochromic compoundsdisclosed herein can be used alone or in conjunction with anotherconventional organic photochromic compound (as discussed above), inamounts or ratios such that the organic host material into which thephotochromic compounds are incorporated, or onto which the organic hostmaterials are applied, can exhibit a desired color or colors, either inan activated or a “bleached” state. Thus the amount of the photochromiccompounds used is not critical provided that a sufficient amount ispresent to produce a desired photochromic effect. As used herein, theterm “photochromic amount” refers to the amount of the photochromiccompound necessary to produce the desired photochromic effect.

Another non-limiting embodiment provides a photochromic articlecomprising a substrate, and an at least partial coating of a coatingcomposition having a photochromic amount of a photochromic compound ofthe present invention connected to at least a portion of at least onesurface thereof of the substrate. Further, although not limiting herein,at least a portion of the at least partial coating can be at leastpartially set. As used herein the term “set” means to fix in a desiredorientation.

For example, according to the above-mentioned non-limiting embodiment,the coating composition can be chosen from, without limitation,polymeric coating compositions, paints, and inks. Further, in additionto the photochromic compounds disclosed herein, the coating compositionsaccording to various non-limiting embodiments can further comprise atleast one other conventional organic photochromic compounds having atleast one activated absorption maxima within the range of 300 nm to 1000nm, inclusive.

Non-limiting examples of suitable substrates to which the coatingcomposition comprising the photochromic amount of the photochromiccompounds can be applied include glass, masonry, textiles, ceramics,metals, wood, paper and polymeric organic materials. Non-limitingexamples of suitable polymeric organic materials are set forth above.

Still other non-limiting embodiments provide optical elements comprisinga substrate and an at least partial coating comprising at least onephotochromic compound of the present invention connected to at least aportion of the substrate. Non-limiting examples of optical elementsinclude, ophthalmic elements, display elements, windows, and mirrors.For example, according to one non-limiting embodiment, the opticalelement is an ophthalmic element, and the substrate is an ophthalmicsubstrate chosen from corrective and non-corrective lenses, partiallyformed lenses, and lens blanks.

Although not limiting herein, the optical elements according to variousnon-limiting embodiments disclosed herein can comprise any amount of thephotochromic compound necessary to achieve the desired opticalproperties, such as but not limited to, photochromic properties anddichroic properties.

Other non-limiting examples of substrates that are suitable for use inconjunction with the foregoing non-limiting embodiment include untintedsubstrates, tinted substrates, photochromic substrates,tinted-photochromic substrates, linearly polarizing substrates,circularly polarizing substrates, elliptically polarizing substrates,and reflective substrates. As used herein with reference to substratesthe term “untinted” means substrates that are essentially free ofcoloring agent additions (such as, but not limited to, conventionaldyes) and have an absorption spectrum for visible radiation that doesnot vary significantly in response to actinic radiation. Further, withreference to substrates the term “tinted” means substrates that have acoloring agent addition (such as, but not limited to, conventional dyes)and an absorption spectrum for visible radiation that does not varysignificantly in response to actinic radiation.

As used herein the term “linearly polarizing” with reference tosubstrates refers to substrates that are adapted to linearly polarizeradiation (i.e., confine the vibrations of the electric vector of lightwaves to one direction). As used herein the term “circularly polarizing”with reference to substrates refers to substrates that are adapted tocircularly polarize radiation. As used herein the term “ellipticallypolarizing” with reference to substrates refers to substrates that areadapted to elliptically polarize radiation. As used herein with the term“photochromic” with reference to substrates refers to substrates havingan absorption spectrum for visible radiation that vanes in response toat least actinic radiation and is thermally reversible. Further, as usedherein with reference to substrates, the term “tinted-photochromic”means substrates containing a coloring agent addition as well as aphotochromic compound, and having an absorption spectrum for visibleradiation that varies in response to at least actinic radiation and isthermally reversible. Thus for example, in one non-limiting embodiment,the tinted-photochromic substrate can have a first color characteristicof the coloring agent and a second color characteristic of thecombination of the coloring agent and the photochromic compound whenexposed to actinic radiation.

One specific non-limiting embodiment provides an optical elementcomprising a substrate and an at least partial coating comprising atleast one photochromic compound of the present invention connected to atleast a portion of the substrate. Further, according to thisnon-limiting embodiment, the at least one thermally reversiblephotochromic compound can be a photochromic-dichroic compound having anaverage absorption ratio greater than 2.3 in an activated state asdetermined according to CELL METHOD.

As discussed above, the optical elements according to variousnon-limiting embodiments disclosed herein can be display elements, suchas, but not limited to screens, monitors, and security elements. Forexample, one non-limiting embodiment provides a display elementcomprising a first substrate having a first surface, a second substratehaving a second surface, wherein the second surface of the secondsubstrate is opposite and spaced apart from the first surface of thefirst substrate so as to define a gap; and a fluid material comprisingat least one photochromic compound of the present invention positionedwithin the gap defined by the first surface of the first substrate andthe second surface of the second substrate. Further, the at least onephotochromic compound can be a photochromic-dichroic compound having anaverage absorption ratio greater than 2.3 in an activated state asdetermined according to CELL METHOD.

Further, according to this non-limiting embodiment, the first and secondsubstrates can be independently chosen from untinted substrates, tintedsubstrates, photochromic substrates, tinted-photochromic substrates,linearly polarizing substrates, circularly polarizing substrates,elliptically polarizing substrates and reflective substrates.

Another non-limiting embodiment provides a security element comprising asubstrate and at least one photochromic compound of the presentinvention connected to at least a portion of the substrate. Non-limitingexamples of security elements include security marks and authenticationmarks that are connected to at least a portion of a substrate, such asand without limitation: access cards and passes, e.g., tickets, badges,identification or membership cards, debit cards etc.; negotiableinstruments and non-negotiable instruments e.g., drafts, checks, bonds,notes, certificates of deposit, stock certificates, etc.; governmentdocuments, e.g., currency, licenses, identification cards, benefitcards, visas, passports, official certificates, deeds etc.; consumergoods, e.g., software, compact discs (“CDs”), digital-video discs(“DVDs”), appliances, consumer electronics, sporting goods, cars, etc.;credit cards; and merchandise tags, labels and packaging.

Although not limiting herein, according to this non-limiting embodiment,the security element can be connected to at least a portion of asubstrate chosen from a transparent substrate and a reflectivesubstrate. Alternatively, according to certain non-limiting embodimentswherein a reflective substrate is required, if the substrate is notreflective or sufficiently reflective for the intended application, areflective material can be first applied to at least a portion of thesubstrate before the security mark is applied thereto. For example, areflective aluminum coating can be applied to the at least a portion ofthe substrate prior to forming the security element thereon. Stillfurther, security element can be connected to at least a portion of asubstrate chosen from untinted substrates, tinted substrates,photochromic substrates, tinted-photochromic substrates, linearlypolarizing, circularly polarizing substrates, and ellipticallypolarizing substrates.

Additionally, according to the aforementioned non-limiting embodimentthe at least one photochromic compound can be a thermally reversiblephotochromic-dichroic compound having an average absorption ratiogreater than 2.3 in the activated state as determined according to CELLMETHOD.

Furthermore, security element according to the aforementionednon-limiting embodiment can further comprise one or more other coatingsor sheets to form a multi-layer reflective security element with viewingangle dependent characteristics as described in U.S. Pat. No. 6,641,874,which is hereby specifically incorporated by reference herein.

The photochromic articles and optical elements described above can beformed by methods known in the art. Although not limiting herein, it iscontemplated that the photochromic compounds disclosed herein can beconnected to a substrate or host by incorporation into the host materialor application onto the host or substrate, such as in the form of acoating.

For example, the photochromic-dichroic compound can be incorporated intoan organic host material by dissolving or dispersing the photochromiccompound within the host material, e.g., casting it in place by addingthe photochromic compound to the monomeric host material prior topolymerization, imbibition of the photochromic compound into the hostmaterial by immersion of the host material in a hot solution of thephotochromic compound or by thermal transfer. As used herein the term“imbibition” includes permeation of the photochromic compound alone intothe host material, solvent assisted transfer of the photochromiccompound into a porous polymer, vapor phase transfer, and other suchtransfer methods.

Additionally, the photochromic compound disclosed herein can be appliedto the organic host material or other substrate as part of a coatingcomposition (as discussed above) or a sheet comprising the photochromiccompound. As used herein the term “coating” means a supported filmderived from a flowable composition, which may or may not have a uniformthickness. As used herein the term “sheet” means a pre-formed filmhaving a generally uniform thickness and capable of self-support.

Non-limiting methods of applying coating compositions comprising thephotochromic compounds disclosed herein include those methods known inthe art for applying coatings, such as, spin coating, spray coating,spray and spin coating, curtain coating, flow coating, dip coating,injection molding, casting, roll coating, wire coating, and overmolding.According to one non-limiting embodiment, a coating comprising thephotochromic compound is applied to a mold and the substrate is formedon top of the coating (i.e., overmolding). Additionally oralternatively, a coating composition without the photochromic compoundcan be first applied to the substrate or organic host material using anyof the aforementioned techniques and thereafter imbibed with thephotochromic compound as described above.

Non-limiting methods of applying sheets comprising the photochromiccompound disclosed herein to a substrate include, for example, at leastone of: laminating, fusing, in-mold casting, and adhesively bonding thepolymeric sheet to the at least a portion of the substrate. As usedherein, the in-mold casting includes a variety of casting techniques,such as but not limited to: overmolding, wherein the sheet is placed ina mold and the substrate is formed (for example by casting) over atleast a portion of the substrate; and injection molding, wherein thesubstrate is formed around the sheet. Further, it is contemplated thatthe photochromic compound can be applied to the sheet as a coating,incorporated into the sheet by imbibition or by other suitable methods,either prior to applying the sheet to the substrate or thereafter.

Moreover, as discussed above, the photochromic compounds disclosedherein can be incorporated or applied alone, or in combination with atleast one other conventional organic photochromic compound, which canalso be applied or incorporated into the host materials and substratesas described above. Additional coatings may be applied to thephotochromic article including other photochromic coatings,anti-reflective coatings, linearly polarizing coatings, transitionalcoatings, alignment layers, primer coatings, adhesive coatings, mirroredcoatings and protective coatings including antifogging coatings, oxygenbarrier coatings and ultraviolet light absorbing coatings.

Various embodiments disclosed herein will now be illustrated in thefollowing non-limiting examples.

EXAMPLES Part I Preparation Example 1 Step 1

2,3-Dimethoxy-7,7-dimethyl-7H-benzo[c]fluoren-5-ol (100.17 grams (g),0.31 mole (mol)), 2,6-dimethylpiperidine (38.93 g, 0.344 mole),tetrahydrofuran (THF) (400 milliliters (mL)) and toluene (400 mL) wereadded to a reaction flask equipped with an addition funnel and acondenser. The resulting mixture was stirred. Ethyl magnesium bromide(240 mL of a 3 Molar solution in hexanes) was added slowly with thecondenser open to the atmosphere. After the addition, about 300 mL ofsolvent was removed by distillation and nitrogen was applied through thecondenser. The remaining mixture was refluxed for about 16 hours. Themixture was then poured into a beaker containing 3 L of water. The pHwas adjusted to about 3 using 12 N hydrochloric acid (HCl). The waterwas decanted and the resulting oily mixture was dissolved in ethylacetate, dried over magnesium sulfate and concentrated. Methylenechloride was added to the mixture to crystallize the product. Theproduct was collected by vacuum filtration and dried in a vacuumdesiccator yielding 57 grams of off-white crystals. A Nuclear MagneticResonance (NMR) spectrum showed that the recovered product had astructure consistent with7,7-dimethyl-3-methoxy-7H-benzo[c]fluorene-2,5-diol.

Step 2

4-Fluorobenzophenone (44.6 g) and anhydrous dimethyl sulfoxide (DMSO)(200 mL) were added to a reaction flask under nitrogen.1-(4-methoxyphenyl)-piperazine (94 g) was added, and the suspension washeated to 160° C. After 2 hours, heat was removed, and the mixture waspoured into 4 liters of water. The precipitate was collected by vacuumfiltration, washed with acetone and dried in vacuum. NMR data showedthat the resulting product (81.5 g), recovered as a white solid, had astructure consistent with4-(4-(4-methoxyphenyl)piperazin-1-yl)benzophenone.

Step 3

The product of Step 2, 4-(4-(4-methoxyphenyl)piperazin-1-yl)benzophenone(80.6 g) and dimethylformamide (DMF) (750 mL, saturated with acetylene)were added to a reaction flask. A sodium acetylide suspension (121 g ofa 18 weight percent slurry in toluene, obtained from Aldrich) was addedto the mixture with stirring. After 30 minutes, the reaction was pouredinto a stirred mixture of deionized water (2 L) and hexanes (500 mL).The solid formed was collected by vacuum filtration and dried in vacuum.An NMR spectrum showed that the final product (85 g), an off-whitepowder, had a structure consistent with1-phenyl-1-(4-(4-methoxyphenylpiperazin-1-yl)phenyl)-prop-2-yn-1-ol.

Step 4

The product of Step 1,7,7-dimethyl-3-methoxy-7H-benzo[c]fluorene-2,5-diol (1.93 g, 6.3millimole (mmole)), and the product of Step 3,1-phenyl-1-(4-(4-methoxyphenylpiperazin-1-yl)phenyl)-prop-2-yn-1-ol(2.76 g, 6.9 mmole), trimethyl orthoformate (1.47 g, 13.9 mmole),pyridinium p-toluenesulfonate (0.08 g, 0.3 mmole) and chloroform (40 mL)was added to a reaction flask, stirred and refluxed for 6 hours. Theresulting product was kept stirring at room temperature (approximately23° C.) for 12 hours. The solution was then concentrated to a smallervolume until the product started to foam. Methanol, 250 mL was added toprecipitate the product. A black solid (4.1 g) was obtained after vacuumfiltration. The recovered product was identified by NMR as having astructure consistent with3-phenyl-3-(4-(4-methoxyphenylpiperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-hydroxyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Step 5

The product of Step 4,3-phenyl-3-(4-(4-methoxyphenylpiperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-hydroxyl-indeno[2′,3′:3,4]naphtho[1,2-b]pyran(3.1 g, 4.5 mmole), and pyridine (30 mL) at 0° C. were added to areaction flask and stirred, trifluoromethanesulfonic acid anhydride(1.53 g, 5.4 mmole) was added in one portion. The resulting reaction wasstirred for 4 hours at room temperature and then poured into a beakercontaining water (500 mL). The precipitated product was collected byvacuum filtration. It was dissolved in chloroform followed byprecipitation from methanol. An NMR spectrum showed that the recoveredproduct (3.3 g), a green solid, had a structure consistent with3-phenyl-3-(4-(4-methoxyphenylpiperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-trifluoromethanesulfonyloxy-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 2

The product of Example 1,3-phenyl-3-(4-(4-methoxyphenylpiperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-trifluoromethanesulfonyloxy-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran(11.37 g, 13.9 mmole), zinc cyanide (1.71 g, 14.6 mmole), zinc acetate(0.1 g, 0.56 mmole), zinc (0.036 g, 0.56 mmole), dimethylformamide (DMF)(40 mL), deionized water (0.4 mL), 1,1′-bis(diphenylphosphino)ferrocene(0.02 g, 0.035 mmole) and tris(dibenzylideneacetone)dipalladium (0.013g, 0.014 mmole) was added to a reaction flask degassed and stirred underthe protection of nitrogen. The reaction flask was kept in an oil bathmaintained at a temperature of 90-100° C. After 12 hours1,1′-bis(diphenylphosphino)ferrocene (0.05 g) andtris(dibenzylideneacetone)dipalladium (0.032 g) was added. After 24 morehours, the reaction mixture was diluted with ethyl acetate (300 mL),filtered through Grade 60, 230-400 mesh silica gel available from FisherScientific, and concentrated. The resulting product was purified byflash chromatography using ethyl acetate/hexanes with a volume ratio of1/4. A green solid (5.6 g) was recovered as the product. An NMR spectrumshowed that the product had a structure consistent with3-phenyl-3-(4-(4-methoxyphenylpiperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-cyano-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 3

The product of Example 1,3-phenyl-3-(4-(4-methoxyphenylpiperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-trifluoromethanesulfonyloxy-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran (1.71 g, 2.1 mmole),2-methyl-3-butyn-2-ol (0.26 g, 3.1 mmole),bis(triphenylphosphine)palladium(II) chloride 0.015 g, 0.02 mmole),copper (I) iodide (8 mg, 0.04 mmole), triphenyl phosphine (22 mg, 0.08mmole) and diisopropyl amine (10 ml) was added to a reaction flask,degassed, protected by dry nitrogen and stirred at 70-80° C. for about12 hours. The reaction mixture was poured into cold water (100 mL) andthe resulting precipitate was collected. The resulting product was thenpurified by flash chromatography using ethyl acetate/hexanes with avolume ratio of 3/7. A green solid (1.18 g) was recovered as theproduct. An NMR spectrum showed that the product had a structureconsistent with3-phenyl-3-(4-(4-methoxyphenylpiperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-(2-hydroxy-2-methyl-3-butyn-4-yl)-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 4 Step 1

3′-Bromoacetophenone (200.0 g, 1 mol), dimethyl succinate (190 g, 1.3mmole) and toluene (800 mL) were added to a 3 L flask and placed onmagnetic stir under nitrogen. Potassium t-butoxide (123 g, 1.1 mole) wasadded over a one hour period. The temperature was controlled to lessthan 40° C. After one hour, the resulting reaction mixture was pouredinto 1 L of water and stirred for 15 minutes. The layers were separated,and the aqueous layer was acidified to pH 4 while stirring. Ethylacetate (500 mL) was added to the stirring mixture, and the layers wereseparated after 15 minutes. The solvent was removed by rotaryevaporator, and the resulting product was isolated as translucent brownoil. The oil was not purified but used directly in the next step.

Step 2

Acetic anhydride (300 ml) was added to a 2 L flask containing theproduct from Step 1 (220 g, 0.7 mole). The solution was heated to 100°C. under nitrogen. After 4 hours, the resulting reaction wasconcentrated to brown oil. The oil was dissolved in methylene chloride,washed twice with sodium bicarbonate saturated water, dried overmagnesium sulfate and concentrated. The resulting oil was crystallizedfrom ether (34 g crystals were obtained). The remaining crude oil (102g) was used in next step.

Step 3

Methanol (300 mL) was added to a 1 L flask containing the crude oil fromStep 2 (102 g). Concentrated HCl (1 mL) was added and the solution washeated to reflux temperature and maintained there for 4 hours. More ofthe concentrated HCL (1 mL) was added and the reaction mixture wasrefluxed another 4 hours. Afterwards, the reaction mixture wasconcentrated into oil. The crude product was purified by crystallizationfrom acetonitrile and t-butyl methyl ether. A white solid was obtainedas the product (40 g), which was identified by NMR as having a structureconsistent with 6-bromo-1-hydroxy-4-methyl-3-naphthoic acid methylester.

Step 4

A mixture of 6-bromo-1-hydroxy-4-methyl-3-naphthoic acid methyl ester (5g, 17 mmole), zinc cyanide (2.2 g, 19 mmole), zinc acetate (0.13 g, 0.7mmole), zinc (0.046 g, 0.7 mmole), DMF (100 mL), water (1 mL),1,1′-bis(diphenylphosphino)ferrocene (0.047 g, 0.085 mmole) andtris(dibenzylideneacetone)dipalladium (0.031 g, 0.034 mmole) was addedto a reaction flask, degassed and stirred under the protection ofnitrogen. The reaction mixture was heated to 70° C. After 24 hours,1,1′-bis(diphenylphosphino)ferrocene (0.5 g) andtris(dibenzylideneacetone)-dipalladium (0.03 g) were added and thereaction was maintained under the same conditions for 15 hours. Theresulting suspension was vacuum filtered to remove zinc. The solutionwas poured into 200 mL water and stirred for 15 minutes. The solidproduct was collected by vacuum filtration and recrystallized from ethylacetate The recovered product, 1.1 g of yellow-white crystals, wasidentified by NMR as having a structure consistent with6-cyano-1-hydroxy-4-methyl-3-naphthoic acid methyl ester.

Step 5

The product of Step 4, 6-cyano-1-hydroxy-4-methyl-3-naphthoic acidmethyl ester (1 g, 4 mmole), the product of Step 3 of Example 1,1-phenyl-1-(4-(4-methoxyphenylpiperazin-1-yl)phenyl)-prop-2-yn-1-ol (1.9g, 4.8 mmole), pyridinium p-toluenesulfonate (0.2 g, 0.8 mmole) andchloroform (100 mL) was heated to reflux. After 4 hours, the incompletereaction mixture was concentrated to an oil and purified by columnseparation using hexanes:ethyl acetate with a volume ratio of 4:1. Theproduct was further purified by recrystallization from ethyl acetate. Apink-white solid (0.3 g) was obtained as the desired product. Theproduct was confirmed by NMR as having a structure consistent with2-phenyl-2-[4-(4-Methoxy-phenyl)-piperazin-1-yl]-phenyl-5-methoxycarbonyl-6-methyl-8-cyano-2H-naphtho[1,2-b]pyran.

Example 5 Step 1

Toluene (3.0 L) was added under nitrogen to a suitable 16 liter reactor.3-Bromoacetophenone (600 grams) and dimethyl succinate (512 mL) wereadded to the reactor. Potassium tert-pentoxide in an approximately 25weight percent solution in toluene (2,640 mL) was added to the reactorat a rate of approximately 50 mL per minute while keeping thetemperature below 35° C. After completion of the addition, the resultingreaction mixture was stirred for 1 to 3 hours until the amount of3-bromoacetophenone was less than 1 weight percent as determined by HighPerformance Liquid Chromatography (HPLC). The reaction mixture wascooled to 15° C. and water (4 L) was added. The resulting mixture waswarmed to 20-25° C. and stirred for 30 minutes. After phase separation,the bottom aqueous phase was collected. Toluene (1.5 L) was added andstirring continued for 15 minutes. After phase separation, the bottomaqueous phase was collected and methylene chloride (4 L) was added toit. The resulting mixture was maintained at a temperature of 20-25° C.and 6N HCl (850-900 mL) was added while stirring to reduce the pH toapproximately 2.0. The resulting mixture was stirred for 20 minutes.After phase separation, the bottom organic phase was collected, washedwith water (2 L) and filtered through a plug of 200 grams of silica witha half inch (1.27 cm) thick layer of magnesium sulfate on the top. Theplug was rinsed with 1.5 L methylene chloride and then with a 30 weightpercent ethyl acetate in methylene chloride mixture until all theproduct as determined by Thin Layer Chromatography (TLC). The resultingsolution was distilled to a volume of 4 L and transferred to a 6 Lreactor as a crude solution without the isolation of pure product.

Step 2

Xylene (1.8 L) was added to the crude solution from Step 1 and theresulting mixture was distilled at 100° C. to remove the methylenechloride. Afterwards, the temperature of the reactor contents wasreduced to 60° C. and 4-dimethylamino pyridine (3.6 grams) and aceticanhydride (615 grams) were added to the reactor. The resulting mixturewas heated to 120° C. and maintained at that temperature for 24 to 30hours. After the reaction was completed, the reaction mixture was cooledto 70° C. HCl, 10 weight percent, (150 mL) was added through a droppingfunnel while maintaining the reaction mixture temperature below 80° C.The resulting reaction was maintained at 77° C. for 24 to 30 hours.After the reaction was completed, xylene (500 mL) and heptanes (1.2 L)were slowly added to the reaction mixture while it was maintained above65° C. After the addition, the resulting reaction mixture was cooled toabout 20° C. over a period of 3-4 hours. After cooling to 20° C., thereaction mixture was stirred for 6-12 hours for crystallization. Thereaction mixture was cooled to 10° C. and the product (crystals) wasfiltered, washed with 1:1 volume ratio of xylene:heptanes (1-2 L)followed by a wash with heptanes (2-3 L) and dried at 80° C. Theresulting product was confirmed by NMR to have a structure consistentwith 2-methoxycarbonyl-7-bromo-1-methyl-2-naphth-4-ol.

Step 3

To a suitable reactor was added methanol (2.5 L),2-methoxycarbonyl-7-bromo-1-methyl-2-naphth-4-ol, the product of Step 2(250 grams), and water (200 mL). The resulting reaction mixture wasstirred while sodium hydroxide, 50 weight percent, 150 mL was addedslowly through a dropping funnel and the funnel was washed with water(50 mL). The resulting mixture was maintained at 65° C. with stirringfor about 3 hours. After about 3 hours, the temperature of the reactionmixture was increased to 75° C. and methanol (2 L) was distilled off.Water (250 mL) was added to the reaction mixture and the temperature wasincreased to 80° C. while the distillation was continued. Then thereaction mixture was cooled to 15° C. HCl, 10 weight percent, (1.5 L)was added to the reaction mixture while maintaining the temperaturebelow 25° C. Ethyl acetate (2.5 L) was added followed by HCl, 10 weightpercent, (300-400 mL) until a pH of 2.0 was obtained. The lower aqueouslayer was separated and discarded. The organic phase was washed withsodium chloride, 10 weight percent, (1 L) and filtered through a smallplug of Celite and magnesium sulfate. The filtered organic phase wastransferred to a reactor and distilled to a minimum volume. Toluene (1L) was added and the distillation was continued until the mixturereached 100° C. The resulting mixture was cooled to 15° C., stirred for2-3 hours and the crystallized product was filtered. The resultingproduct was washed with 1:1 volume ratio of toluene:heptanes (1 L),followed by a washing with heptanes (1-1.5 L) and dried at 80° C. Theresulting product was confirmed by NMR as having a structure consistentwith 7-bromo-4-hydroxy-1-methyl-2-naphthoic acid.

Step 4

7-Bromo-4-hydroxy-1-methyl-2-naphthoic acid from Step 3 (20.15 g, 74.35mmole), 2-methoxy ethanol (200 mL) and p-toluenesulfonic acid (8.00 g,37.17 mol) were added to a round bottom flask (500 mL) equipped with aDean-Stark apparatus and stirring bar. The mixture was heated to refluxfor 24 h and then cooled to room temperature. The solvent was removedunder vacuum to produce an oily residue. The residue was dissolved inethyl acetate (300 mL) and washed with saturated aqueous sodiumbicarbonate three times, each time with 100 mL. The resulting ethylacetate solution was dried with anhydrous sodium sulfate andconcentrated under vacuum to produce a brown solid (17.4 g). NMRanalysis of the brown solid indicated that the solid has a structureconsistent with 2-methoxyethyl-7-bromo-4-hydroxy-1-methyl-2-naphthoate.

Step 5

1,1-Bis(4-methoxyphenyl)prop-2-yn-1-ol (2.99 g, 11.18 mmole) andp-toulenesulfonic acid (141 mg, 0.74 mmole) were added to a reactionflask containing a chloroform solution of the product from Step 4,2-methoxyethyl-7-bromo-4-hydroxy-1-methyl-2-naphthoate (2.52 g, 7.46mmole). The solution was heated to reflux for 4 hours and then thereaction mixture was cooled and the solvent removed under vacuum toproduce an oily residue. The residue was purified by columnchromatography, using 9:1, based on volume, of a hexane and ethylacetate mixture as the eluant. Fractions containing the desired productwere grouped and concentrated under vacuum to produce an oily residue(3.06 g). NMR analysis of the residue indicated a structure that wasconsistent with2,2-bis(4-methoxyphenyl)-5-methoxyethylcarbonyl-6-methyl-8-bromo-2H-naphtho[1,2-b]pyran.

Step 6

To a reaction flask containing2,2-bis(4-methoxyphenyl)-5-methoxyethylcarbonyl-6-methyl-8-bromo-2H-naphtho[1,2-b]pyranfrom Step 5 (2.89 g, 4.91 mmole) and vinylboronic acid pinacol ester (1mL, 5.89 mmole) in a 1:1 mixture of THF (25 mL) and water (25 mL) wasadded potassium fluoride (4.56 g, 78.62 mmole). The solution wasdegassed by bubbling nitrogen for 10 min. To the degassed solutionbis(triphenylphosphine)palladium(II) chloride (0.34 g, 0.49 mmole) wasadded. The solution was heated to reflux for 18 h, cooled to roomtemperature and diluted with ethyl acetate. The mixture was thenfiltered through a bed of Celite and the filtrate was partitioned withethyl acetate and water. The ethyl acetate extract was collected, driedwith anhydrous sodium sulfate and concentrated under vacuum to producean oily residue. The residue was purified by column chromatography using4:1, based on volume, of a hexane and ethyl acetate mixture as theeluant. Fractions that contained the desired product were grouped andconcentrated under vacuum to produce a glassy residue (1.98 g). NMRanalysis of the residue indicated a structure that was consistent with2,2-bis(4-methoxyphenyl)-5-methoxyethylcarbonyl-6-methyl-8-vinyl-2H-naphtho[1,2-b]pyran.

Example 6 Step 1

A mixture of the product of Step 1 of Example 5, (17.4 g, 51.5 mmole)and vinylboronic acid pinacol ester (11.0 mL, 61.8 mmole) in 1:1 mixtureof THF (250 mL) and water (250 mL) was added potassium fluoride (48.0 g,824 mmole). The solution was degassed by bubbling nitrogen for 20 min.To the degassed solution bis(triphenylphosphine)palladium(II) chloride(1.81 g, 2.58 mmole) was added. The solution was heated to reflux for 20h, the reaction mixture was cooled to room temperature and diluted withethyl acetate. The mixture was then filtered through a bed of Celite andthe filtrate was partitioned with ethyl acetate and water. The ethylacetate extract was collected, dried with anhydrous sodium sulfate andconcentrated in vacuo to afford an oily residue. The residue waspurified by column chromatography using 4:1 hexane and ethyl acetatemixture as the eluant. Fractions that contained the desired product weregrouped and concentrated under vacuum to produce a brown solid (11.5 g).NMR analysis of the brown solid indicated a structure that wasconsistent with 2-methoxyethyl 7-vinyl-4-hydroxy-1-methyl-2-naphthoate.

Step 2

The product from Step 1,2-methoxyethyl-7-vinyl-4-hydroxy-1-methyl-2-naphthoate (11.55 g, 40.38mmole) was added to a reaction flask containing methylene chloride (200mL) and pyridine (7.00 mL, 80.76 mmole) was added. The mixture wasstirred for 5 min. and triisopropylsilyl trifluoromethane sulfonate(16.30 mL, 60.57 mmole) was slowly added. The mixture was stirred for 30min at room temperature, poured into ice cold water (500 mL) and stirredfor 10 min. The mixture was partitioned and the methylene chloridesolution was collected, dried with anhydrous sodium sulfate andconcentrated under vacuum to produce an oily residue. The residue waspurified using a silica plug with a 19:1, volume basis, of a hexane andethyl acetate mixture. Fractions containing the desired material weregrouped and concentrated under vacuum to produce a colorless oil (17.85g). NMR analysis indicated a structure that was consistent with2-methoxyethyl-7-vinyl-4-(triisopropylsilyloxy)-1-methyl-2-naphthoate.

Step 3

The product of Step 2,2-methoxyethyl-7-vinyl-4-(triisopropylsilyloxy)-1-methyl-2-naphthoate(17.85 g, 40.38 mmole) was added to a reaction flask containingt-butanol (121 mL) and water (283 mL) and cooled to 0° C. A solution ofpotassium permanganate (19.35 g, 122.49 mmole) in water (180 mL) wasadded slowly to the reaction flask. The pH of the solution was adjustedto 8-10 by the addition of aqueous sodium carbonate. The ice bath wasremoved and the reaction mixture was warmed to room temperature andstirred for 4 hours. The resulting mixture was filtered through a bed ofCelite and the filtrate was carefully acidified to pH 4 by the additionof 10 weight percent aqueous hydrochloric acid. The resulting aqueoussolution was extracted with ethyl acetate three times, each time with300 mL, and the organic layer was collected, dried with anhydrous sodiumsulfate, and concentrated under vacuum to produce an oily residue. Theoily residue was purified through a silica plug using a 4:1, volumebasis, of an ethyl acetate and hexane mixture. Fractions containing thedesired material were grouped and concentrated under vacuum to produce ayellow solid (9.14 g). NMR analysis indicated a structure that wasconsistent with7-((2-methoxyethoxy)carbonyl)-8-methyl-5-(triisopropylsilyloxy)-2-naphthoicacid.

Step 4

The product of Step 3,7-((2-methoxyethoxy)carbonyl)-8-methyl-5-(trisopropylsilyloxy)-2-naphthoicacid (1.17 g, 2.54 mmole) was added to a reaction flask containingmethylene chloride (10 mL). Methanol (0.09 mL, 2.12 mmole) was addedfollowed by dimethylamino pyridine (0.04 g, 0.33 mmole) and N,N′-dicyclohexylcabodiimide (0.53 g, 2.57 mmole). The mixture was stirredfor 1 h at room temperature. The resulting mixture was diluted withmethylene chloride and filtered. The filtrate was collected andconcentrated under vacuum to produce a yellow solid that was not furtherpurified. The yellow solid was added to a reaction flask containingtetrahydrofuran (10 mL) and water (10 mL). Potassium fluoride (0.35 g,6.03 mmole) was added and the mixture stirred at room temperature for 20h. The resulting mixture was extracted with ethyl acetate (100 mL) andpartitioned with water. The ethyl acetate extract was collected, driedwith anhydrous sodium sulfate, and concentrated under vacuum to producean oily residue. The residue was dissolved in a minimum amount ofmethylene chloride and hexanes were added until a precipitate formed.The precipitate (0.61 g) was collected by vacuum filtration and washedwith cold hexane. NMR analysis of the precipitate indicated a structurethat was consistent with2-(2-methoxyethyl)-7-methyl-4-hydroxy-1-methylnaphthalene-2,7-dicarboxylate.

Step 5

The product from Step 4,2-(2-methoxyethyl)-7-methyl-4-hydroxy-1-methylnaphthalene-2,7-dicarboxylate(0.61 g, 1.92 mmole), was added to a reaction flask containingchloroform (20 mL). 1,1-Bis(4-methoxyphenyl)prop-2-yn-1-ol (0.77 g, 2.87mmole) and p-toluenesulfonic acid (0.04 g, 0.0.21 mmole) were added. Theresulting solution was heated to reflux and maintained at refluxtemperature for 4 hours. Afterwards, the reaction mixture was cooled andthe solvent removed under vacuum to produce an oily residue. The residuewas purified by column chromatography and eluted with a 4:1, volumebasis, of a hexane and ethyl acetate mixture. Fractions containing thedesired product were grouped and concentrated under vacuum to produce anoily residue (0.76 g). NMR analysis of the residue indicated a structurethat was consistent with2,2-bis(4-methoxyphenyl)-5-methoxyethylcarbonyl-6-methyl-8-methoxycarbonyl-2H-naphtho-[1.2-b]pyran.

Example 7 Step 1

To a reaction flask containing the product of Step 5 of Example 6,5-(2-methoxyethyl)-8-methyl2,2-bis(4-methoxyphenyl)-6-methyl-2H-naphtho-[1,2-b]pyran-5,8-dicarboxylate(0.56 g, 0.98 mmole) was added tetrahydrofuran (10 mL), methanol (5 mL)and 50 weight percent aqueous sodium hydroxide (3 mL). The mixture wasstirred for 30 min. and then poured into a beaker containing 10 weightpercent aqueous hydrochloric acid (100 mL) solution. The resultingmixture was extracted with ethyl acetate, three times each time with 100mL. The ethyl acetate extracts were collected, dried with anhydroussodium sulfate and concentrated under vacuum to produce an oily residue.The residue was purified using a silica plug eluted with a 19:1, volumebasis, ethyl acetate and methanol mixture. The fractions containing thedesired product were grouped and concentrated under vacuum to producefoam (0.45 g). NMR analysis of the foam indicated a structure that wasconsistent with2,2-bis(4-methoxyphenyl)-5-methoxyethoxycarbonyl-6-methyl-8-hydroxycarbonyl-2H-naphtho[1,2-b]pyran.

Comparative Example 1

A mixture of the product of Example 1,3-phenyl-3-(4-(4-methoxyphenylpiperazin-1-yl)phenyl)-13,13-dimethyl-6-methoxy-7-trifluoromethanesulfonyloxy-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran(0.13 g, 0.16 mmol), potassium carbonate (0.054 g, 0.4 mmole),Tetrakistriphenylphosphine palladium (0) (0.018 g, 0.016 mmole),2-butanol (3 mL) and THF (1 mL) was added to a reaction flask, degassedand stirred under the protection of nitrogen. The reaction mixture washeated to reflux. After 3 hours, reaction mixture was diluted with 100mL ethyl acetate, washed with water, dried over magnesium sulfate andconcentrated. The crude product was purified by flash chromatography(3/7 ethyl acetate/hexanes). The product was further purified bydissolution into methylene chloride followed by precipitation frommethanol. A grey solid (0.08 g) was obtained. It was identified by NMRas having a structure consistent with3-phenyl-3-(4-(4-methoxyphenylpiperazin-1-yl)phenyl)-13,13-dimethyl-6-3H,13H-methoxy-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Comparative Example 2 Step 1

A mixture of the product of Step 3 of Example 6,7-((2-methoxyethoxy)-carbonyl)-8-methyl-5-(triisopropylsilyloxy)-2-naphthoicacid (2.3 g, 7.8 mmole), potassium carbonate (4.4 g, 32 mmole),tetrakistriphenylphosphine palladium (0) (0.52 g, 0.44 mmole), 2-butanol(20 ml) and methanol (10 ml) was added to a reaction flask, degassed andstirred under the protection of nitrogen. The reaction mixture washeated to reflux. After 6 hours, reaction mixture was diluted with 100ml ethyl acetate, washed with water, dried over magnesium sulfate,filtered through a thin layer of silica gel and concentrated. A brownishglassy solid (1.7 g) was obtained and used directly in the next step. Itwas identified by NMR as having a structure consistent with1-hydroxy-4-methyl-3-naphthoic acid methyl ester.

Step 2

A mixture of the product of Step 1, 1-hydroxy-4-methyl-3-naphthoic acidmethyl ester (1.6 g, 7.4 mmole),1-phenyl-1-(4-(4-methoxyphenylpiperazin-1-yl)phenyl)-prop-2-yn-1-ol (2.9g, 7.4 mmole), p-tolunesulfonic acid (0.14 g, 0.74 mmol) and methylenechloride (30 mL) was stirred and refluxed for 17 hours. Product in thereaction mixture was then separated by flash chromatography (3/7 ethylacetate/hexanes). The recovered dark red solid was stirred in methanolfor 20 hours. A light yellow solid (1.3 g) was obtained as the desiredproduct. The product was confirmed by NMR as having a structureconsistent with2-phenyl-2-[4-(4-Methoxy-phenyl)-piperazin-1-yl]-phenyl-5-methoxycarbonyl-6-methyl-2H-naphtho[1,2-b]pyran.

Comparative Example 3 Step 1

A mixture of the product of Step 5 of Example 5,2,2-bis(4-methoxyphenyl)-5-methoxyethylcarbonyl-6-methyl-8-methoxycarbonyl-2H-naphtho-[1,2-b]pyran(1.37 g, 2.33 mmole), potassium carbonate (1.29 g, 9.32 mmole),2-butanol (10 mL) and methanol (10 mL) were added to a round bottomflask (100 mL) and degassed for 10 min. Tetrakistriphenylphosphinepaladium (0) (0.13 g, 0.12 mmol) was added and the mixture was heated toreflux under nitrogen. The mixture was maintained at reflux temperaturefor 4 hours. The resulting mixture was diluted with ethyl acetate,washed with water, dried with anhydrous sodium sulfate and concentratedunder vacuum to produce an oily residue. The residue was purified byflash column chromatography using 9:1, volume basis, of a hexane andethyl acetate mixture as the eluant. Fractions that contained thedesired product were grouped and concentrated under vacuum to produce ared oily residue (0.95 g). The product was confirmed by NMR as having astructure consistent with 2,2-bis(4-methoxyphenyl)-5-((2-methoxyethoxy)carbonyl-6-methyl-2H-naphtho[1,2-b]pyran.

Part II Testing

The photochromic performance of the photochromic materials of Examples1-7, and Comparative Examples (CE) 1, 2 and 3 were tested using theoptical bench set-up described below. Each of the photochromic materialswere incorporated into methacrylate test squares as describedhereinafter. CE 1 was included for comparison to Examples 1-3 and CE 2was included for comparison to Example 4 and CE 3 was included forcomparison to Examples 5-7. It will be appreciated by those skilled inthe art that the photochromic materials of Examples 1-7 and CE1-3 may bemade in accordance with the teachings and examples disclosed herein withappropriate modifications, which will be readily apparent to thoseskilled in the art upon reading the present disclosure. Further, thoseskilled in the art will recognize that various modifications to thedisclosed methods, as well as other methods, may be used in making thephotochromic materials of Examples 1-7 without deviating from the scopeof the present disclosure as set forth in the specification and claimsherein.

A quantity of the photochromic material to be tested, calculated toyield a 1.5×10⁻³ M solution was added to a flask containing 50 grams ofa monomer blend of 4 parts ethoxylated bisphenol A dimethacrylate (BPA2EO DMA), 1 part poly(ethylene glycol) 600 dimethacrylate, and 0.033weight percent 2,2′-azobis(2-methyl propionitrile) (‘AlBN’). Thephotochromic material was dissolved into the monomer blend by stirringand gentle heating. After a clear solution was obtained, it was vacuumdegassed before being poured into a flat sheet mold having the interiordimensions of 2.2 mm×6 inches (15.24 cm)×6 inches (15.24 cm). The moldwas sealed and placed in a horizontal air flow, programmable ovenprogrammed to increase the temperature from 40° C. to 95° C. over a 5hour interval, hold the temperature at 95° C. for 3 hours, and thenlower the temperature to 60° C. for at least 2 hours. After the mold wasopened, the polymer sheet was cut using a diamond blade saw into 2 inch(5.1 cm) test squares.

The test squares incorporating the photochromic materials prepared asdescribed above were tested for photochromic response on an opticalbench. Prior to testing on the optical bench, the photochromic testsquares were exposed to 365 nm ultraviolet light for about 30 minutes tocause the photochromic materials therein to transform from theunactivated ground (or bleached) state to an activated (or colored)state, and then placed in a 75° C. oven for about 15 minutes to allowthe photochromic material to revert back to the unactivated state. Thetest squares were then cooled to room temperature, exposed tofluorescent room lighting for at least 2 hours, and then kept covered(that is, in a dark environment) for at least 2 hours prior to testingon an optical bench maintained at 23° C. The bench was fitted with a300-watt xenon arc lamp, a remote controlled shutter, a Melles Griot KG23 mm filter that modifies the UV and IR wavelengths and acts as aheat-sink, neutral density filter(s), and a sample holder, situatedwithin a 23° C. water bath, in which the square to be tested wasinserted. The sample holder and sample were positioned at a small angle(approximately 31°) to the activation beam produced by the 300 Wattxenon arc lamp. A collimated beam of light from a tungsten lamp waspassed through the sample square normal to the square and 31° to thatactivation beam. After passing through the square, the light from thetungsten lamp was directed to a collection (integration) sphere, wherethe light was blended, and on to an Ocean Optics S2000 spectrometerwhere the spectrum of the measuring beam was collected and analyzed. Theλ_(max-vis) is the wavelength in the visible spectrum at which themaximum absorption of the activated (colored) form of the photochromicmaterial in the test square occurs. The λ_(max-vis) wavelength wasdetermined by testing the photochromic test squares in a Varian Cary4000 UV-Visible spectrophotometer.

The saturated optical density (“Sat'd OD”) for each test square wasdetermined by opening the shutter from the xenon lamp and measuring thetransmittance at λ_(max-vis) before and after exposing the test chip toUV radiation for 30 minutes. This Sat'd OD at λ_(max-vis) was calculatedfrom the initial and activated spectra measured by the S2000spectrometer on the optical bench. The Sensitivity is a measure of howquickly the photochromic initially begins to activate and is calculatedas 12 times the optical density achieved at 5 seconds of activation. TheFade Rate, as measured by the fade half life (i.e., T½), is the timeinterval in seconds for the absorbance of the activated form of thephotochromic material in the test squares to reach one half of the Sat'dOD absorbance value at room temperature (23° C.), after removal of thesource of activating light. The results are recorded in Table 1.

TABLE 1 Photochromic Performance Test Results Example λ_(max-vis)Sensitivity ΔOD @ T½ Number (nm) ΔOD/MIN Saturation seconds 1 601 0.410.68 179 2 631 0.67 0.70 92 3 609 0.65 1.19 252 4 583 0.33 0.25 49 5 5070.26 0.36 212 6 526 0.41 0.23 28 7 522 0.42 0.23 27 CE-1 600 0.61 1.34358 CE-2 542 0.31 0.77 224 CE-3 508 0.27 0.29 60

It is to be understood that the present description illustrates aspectsof the invention relevant to a clear understanding of the invention.Certain aspects of the invention that would be apparent to those ofordinary skill in the art and that, therefore, would not facilitate abetter understanding of the invention have not been presented in orderto simplify the present description. Although the present invention hasbeen described in connection with certain embodiments, the presentinvention is not limited to the particular embodiments disclosed, but isintended to cover modifications that are within the spirit and scope ofthe invention, as defined by the appended claims.

1. A photochromic material represented by one of the following graphicformulae:

wherein: (A) each substituent Q independently comprises —N₃, —CN,—COOR′, —CCR′, —C(R′)C(R′)R′, —OCOR′, —OCOOR′, —SR′, —OSO₂R′″, and/or—CONHR′, wherein R′ independently comprises hydrogen, an unsubstitutedor substituted alkyl group having from 1 to 18 carbon atoms, anunsubstituted or substituted aryl group, an unsubstituted or substitutedalkene or alkyne group having from 2 to 18 carbon atoms, wherein saidsubstituents are chosen from halo and hydroxyl and R′″ comprises —CF₃ ora perfluorinated alkyl group having from 2 to 18 carbon atoms; (B) eachi is an integer chosen from 0 to the total number of available positionsand each R is independently chosen for each occurrence from: (a) a grouprepresented by B described hereinafter; (b) —C(O)X₂₄, wherein X₂₄ ischosen from a lengthening agent L, hydroxy, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy,phenyl that is unsubstituted or mono-substituted with C₁-C₁₈ alkyl orC₁-C₁₈ alkoxy, amino that is unsubstituted, mono- or di-substituted withat least one of C₁-C₁₈ alkyl, phenyl, benzyl, and naphthyl; (c) —OX₇ and—N(X₇)₂; wherein X₇ is chosen from: (i) a lengthening agent L, hydrogen,C₁-C₁₈ alkyl, C₁-C₁₈ acyl, phenyl(C₁-C₁₈)alkyl, mono(C₁-C₁₈)alkylsubstituted phenyl(C₁-C₁₈)alkyl, mono(C₁-C₁₈)alkoxy substitutedphenyl(C₁-C₁₈)alkyl; C₁-C₁₈ alkoxy(C₁-C₁₈)alkyl; C₃-C₁₀ cycloalkyl;mono(C₁-C₁₈)alkyl substituted C₃-C₁₀ cycloalkyl, C₁-C₁₈ haloalkyl,allyl, benzoyl, mono-substituted benzoyl, naphthoyl or mono-substitutednaphthoyl, wherein each of said benzoyl and naphthoyl substituents areindependently chosen from C₁-C₁₈ alkyl, and C₁-C₁₈ alkoxy; (ii)—CH(X₈)X₉, wherein X₈ is chosen from a lengthening agent L, hydrogen orC₁-C₁₈ alkyl; and X₉ is chosen from a lengthening agent L, —CN, —CF₃, or—COOX₁₀, wherein X₁₀ is chosen from a lengthening agent L, hydrogen orC₁-C₁₈ alkyl; (iii) —C(O)X₆, wherein X₆ is chosen from at least one of:a lengthening agent L, hydrogen, C₁-C₁₈ alkoxy, phenoxy that isunsubstituted, mono- or di-substituted with C₁-C₁₈ alkyl or C₁-C₁₈alkoxy, an aryl group that is unsubstituted, mono- or di-substitutedwith C₁-C₁₈ alkyl or C₁-C₁₈ alkoxy, an amino group that isunsubstituted, mono- or di-substituted with C₁-C₁₈ alkyl, and aphenylamino group that is unsubstituted, mono- or di-substituted withC₁-C₁₈ alkyl or C₁-C₁₈ alkoxy; or (iv) tri(C₁-C₁₈)alkylsilyl,tri(C₁-C₁₈)alkylsilyloxy, tri(C₁-C₁₈)alkoxysilyl,tri(C₁-C₁₈)alkoxysilyloxy, di(C₁-C₁₈)alkyl(C₁-C₁₈ alkoxy)silyl,di(C₁-C₁₈)alkyl(C₁-C₁₈ alkoxy)silyloxy, di(C₁-C₁₈)alkoxy(C₁-C₁₈alkyl)silyl or di(C₁-C₁₈)alkoxy(C₁-C₁₈ alkyl)silyloxy; (d) —SX₁₁;wherein X₁₁ is chosen from a lengthening agent L, hydrogen, C₁-C₁₈alkyl, C₁-C₁₈ haloalkyl, an aryl group that is unsubstituted, or mono-or di-substituted with C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, or halogen; (e) anitrogen containing ring represented by Formula i:

wherein (i) n is an integer chosen from 0, 1, 2, and 3, and each U isindependently chosen for each occurrence from —CH₂—, —CH(X₁₂)—,—C(X₁₂)₂—, —CH(X₁₃)—, —C(X₁₃)₂—, and —C(X₁₂)(X₁₃)—, wherein X₁₂ ischosen from a lengthening agent L and C₁-C₁₂ alkyl, and X₁₃ is chosenfrom a lengthening agent L, phenyl and naphthyl, and (ii) U′ is chosenfrom U, —O—, —S—, —S(O)—, —NH—, —N(X₁₂)— or —N(X₁₃)—, and m is aninteger chosen from 1, 2, and 3; (f) the group represented by Formula iior iii;

wherein X₁₄, X₁₅, and X₁₆ are independently chosen for each occurrencefrom a lengthening agent L, hydrogen, C₁-C₁₈ alkyl, phenyl or naphthyl,or X₁₄ and X₁₅ together form a ring of 5 to 8 carbon atoms; p is aninteger chosen from 0, 1, or 2, and X₁₇ is independently chosen for eachoccurrence from a lengthening agent L, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, orhalogen; (g) immediately adjacent R groups together form a grouprepresented by Formula vii, viii, or ix:

wherein (i) W and W′ are independently chosen for each occurrence from—O—, —N(X₇)—, —C(X₁₄)—, and —C(X₁₇)—; (ii) X₁₄, X₁₅ and X₁₇, whereinX₁₄, and X₁₅ are independently chosen for each occurrence from alengthening agent L, hydrogen, C₁-C₁₈ alkyl, phenyl or naphthyl, or X₁₄and X₁₅ together form a ring of 5 to 8 carbon atoms; and X₁₇ isindependently chosen for each occurrence from a lengthening agent L,C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, or halogen; and (iii) q is an integerchosen from 0, 1, 2, 3, and 4; and (h) a lengthening agent L representedby:—[S₁]_(c)-[Q₁-[S₂]_(d)]_(d′)-[Q₂-[S₃]_(e)]_(e′)-[Q₃-[S₄]_(f)]_(f′)—S₅—Pwherein: (i) each Q₁, Q₂, and Q₃ is independently chosen for eachoccurrence from: a divalent group chosen from: an unsubstituted or asubstituted aromatic group, an unsubstituted or a substituted alicyclicgroup, an unsubstituted or a substituted heterocyclic group, andmixtures thereof, wherein substituents are chosen from: a grouprepresented by P, liquid crystal mesogens, halogen, poly(C₁-C₁₈ alkoxy),C₁-C₁₈ alkoxycarbonyl, C₁-C₁₈ alkylcarbonyl, C₁-C₁₈ alkoxycarbonyloxy,aryloxycarbonyloxy, perfluoro(C₁-C₁₈)alkoxy,perfluoro(C₁-C₁₈)alkoxycarbonyl, perfluoro(C₁-C₁₈)alkylcarbonyl,perfluoro(C₁-C₁₈)alkylamino, di-(perfluoro(C₁-C₁₈)alkyl)amino,perfluoro(C₁-C₁₈)alkylthio, C₁-C₁₈ alkylthio, C₁-C₁₈ acetyl,C₃-C₁₀cycloalkyl, C₃-C₁₀ cycloalkoxy, a straight-chain or branchedC₁-C₁₈ alkyl group that is mono-substituted with cyano, halo, or C₁-C₁₈alkoxy, or poly-substituted with halo, and a group comprising one of thefollowing formulae: -M(T)_((t-1)) and -M(OT)_((t-1)), wherein M ischosen from aluminum, antimony, tantalum, titanium, zirconium andsilicon, T is chosen from organofunctional radicals, organofunctionalhydrocarbon radicals, aliphatic hydrocarbon radicals and aromatichydrocarbon radicals, and t is the valence of M; (ii) c, d, e, and fareeach independently chosen from an integer ranging from 0 to 20,inclusive; and each S₁, S₂, S₃, S₄, and S₅ is independently chosen foreach occurrence from a spacer unit chosen from: (1) —(CH₂)_(g)—,—(CF₂)_(h)—, —Si(CH₂)_(g)—, —(Si[(CH₃)₂]O)_(h)—, wherein g isindependently chosen for each occurrence from 1 to 20; h is a wholenumber from 1 to 16 inclusive; (2) —N(Z)—, —C(Z)═C(Z)—, —C(Z)═N—,—C(Z′)—C(Z′)— or a single bond, wherein Z is independently chosen foreach occurrence from hydrogen, C₁-C₁₈ alkyl, C₃-C₁₀ cycloalkyl and aryl,and Z′ is independently chosen for each occurrence from C₁-C₁₈ alkyl,C₃-C₁₀ cycloalkyl and aryl; and (3) —O—, —C(O)—, —C≡C—, —N═N—, —S—,—S(O)—, —S(OXO)—, —(O)S(O)—, —(O)S(O)O—, —O(O)S(O)O—, or straight-chainor branched C₁-C₂₄ alkylene residue, said C₁-C₂₄ alkylene residue beingunsubstituted, mono-substituted by cyano or halo, or poly-substituted byhalo; provided that when two spacer units comprising heteroatoms arelinked together the spacer units are linked so that heteroatoms are notdirectly linked to each other and when S₁ and S₅ are linked to PC and P,respectively, they are linked so that two heteroatoms are not directlylinked to each other; (iii) P is chosen from: hydroxy, amino, C₂-C₁₈alkenyl, C₂-C₁₈ alkynyl, azido, silyl, siloxy, silylhydride,(tetrahydro-2H-pyran-2-yl)oxy, thio, isocyanato, thioisocyanato,acryloyloxy, methacryloyloxy, 2-(acryloyloxy)ethylcarbamyl,2-(methacryloyloxy)ethylcarbamyl, aziridinyl, allyloxycarbonyloxy,epoxy, carboxylic acid, carboxylic ester, acryloylamino,methacryloylamino, aminocarbonyl, C₁-C₁₈ alkyl aminocarbonyl,aminocarbonyl(C₁-C₁₈)alkyl, C₁-C₁₈ alkyloxycarbonyloxy, halocarbonyl,hydrogen, aryl, hydroxy(C₁-C₁₈)alkyl, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy,amino(C₁-C₁₈)alkyl, C₁-C₁₈ alkylamino, di-(C₁-C₁₈)alkylamino, C₁-C₁₈alkyl(C₁-C₁₈)alkoxy, C₁-C₁₈ alkoxy(C₁-C₁₈)alkoxy, nitro,poly(C₁-C₁₈)alkyl ether, (C₁-C₁₈)alkyl(C₁-C₁₈)alkoxy(C₁-C₁₈)alkyl,polyethyleneoxy, polypropyleneoxy, ethylenyl, acryloyl,acryloyloxy(C₁-C₁₈)alkyl, methacryloyl, methacryloyloxy(C₁-C₁₈)alkyl,2-chloroacryloyl, 2-phenylacryloyl, acryloyloxyphenyl,2-chloroacryloylamino, 2-phenylacryloylaminocarbonyl, oxetanyl,glycidyl, cyano, isocyanato(C₁-C₁₈)alkyl, itaconic acid ester, vinylether, vinyl ester, a styrene derivative, main-chain and side-chainliquid crystal polymers, siloxane derivatives, ethyleneiminederivatives, maleic acid derivatives, fumaric acid derivatives,unsubstituted cinnamic acid derivatives, cinnamic acid derivatives thatare substituted with at least one of methyl, methoxy, cyano and halogen,or substituted or unsubstituted chiral or non-chiral monovalent ordivalent groups chosen from steroid radicals, terpenoid radicals,alkaloid radicals and mixtures thereof, wherein the substituents areindependently chosen from C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, amino, C₃-C₁₀cycloalkyl, C₁-C₁₈ alkyl(C₁-C₁₈)alkoxy, fluoro(C₁-C₁₈)alkyl, cyano,cyano(C₁-C₁₈)alkyl, cyano(C₁-C₁₈)alkoxy or mixtures thereof, or P is astructure having from 2 to 4 reactive groups or P is an unsubstituted orsubstituted ring opening metathesis polymerization precursor; and (iv)d′, e′ and f′ are each independently chosen from 0, 1, 2, 3, and 4,provided that a sum of d′+e′+f′ is at least 1; (C) each B isindependently chosen from: (i) hydrogen, C₁-C₁₈ alkyl, C₂-C₁₈alkylidene, C₂-C₁₈ alkylidyne, vinyl, C₃-C₁₀ cycloalkyl, C₁-C₁₈haloalkyl, allyl, halogen, and benzyl that is unsubstituted ormono-substituted with at least one of C₁-C₁₈ alkyl and C₁-C₁₈ alkoxy;(ii) phenyl that is mono-substituted at the para position with at leastone substituent chosen from: C₁-C₁₈ alkoxy, linear or branched chainC₁-C₂₀ alkylene, linear or branched chain C₁-C₄ polyoxyalkylene, cyclicC₃-C₂₀ alkylene, phenylene, naphthylene, C₁-C₁₈ alkyl substitutedphenylene, mono- or poly-urethane(C₁-C₂₀)alkylene, mono- orpoly-ester(C₁-C₂₀)alkylene, mono- or poly-carbonate(C₁-C₂₀)alkylene,polysilanylene, polysiloxanylene and mixtures thereof, wherein the atleast one substituent is connected to an aryl group of a photochromicmaterial; (iii) —CH(CN)₂ and —CH(COOX₁)₂, wherein X₁ is chosen from atleast one of a lengthening agent L, hydrogen, C₁-C₁₈ alkyl that isunsubstituted or mono-substituted with phenyl, phenyl(C₁-C₁₈)alkyl thatis mono-substituted with C₁-C₁₈ alkyl, C₁-C₁₈ haloalkyl or C₁-C₁₈alkoxy, and an aryl group that is unsubstituted, mono- ordi-substituted, wherein each aryl substituent is independently chosenfrom C₁-C₁₈ alkyl and C₁-C₁₈ alkoxy; and lengthening agent L; (iv)—CH(X₂)(X₃), wherein: (I) X₂ is chosen from at least one of alengthening agent L, hydrogen, C₁-C₁₈ alkyl, and an aryl group that isunsubstituted, mono- or di-substituted, wherein each aryl substituent isindependently chosen from C₁-C₁₈ alkyl and C₁-C₁₈ alkoxy; and (2) X₃ ischosen from at least one of —COOX₁, —COX₁, —COX₄, and —CH₂OX₅, wherein:X₄ is chosen from at least one of morpholino, piperidino, amino that isunsubstituted, mono- or di-substituted with C₁-C₁₈ alkyl, and anunsubstituted, mono or di-substituted group chosen from phenylamino anddiphenylamino, wherein each substituent is independently chosen fromC₁-C₁₈ alkyl or C₁-C₁₈ alkoxy; and X₅ is chosen from a lengthening agentL, hydrogen, —C(O)X₂, C₁-C₁₈ alkyl that is unsubstituted ormono-substituted with (C₁-C₁₈)alkoxy or phenyl, phenyl(C₁-C₁₈)alkyl thatis mono-substituted with (C₁-C₁₈)alkoxy, and an aryl group that isunsubstituted, mono- or di-substituted, wherein each aryl substituent isindependently chosen from C₁-C₁₈ alkyl and C₁-C₁₈ alkoxy; (v) anunsubstituted, mono-, di-, or tri-substituted aryl group; 9-julolidinyl;or an unsubstituted, mono- or di-substituted heteroaromatic group chosenfrom pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl,benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl,carbazoyl, benzopyridyl, indolinyl, or fluorenyl; wherein each aryl andheteroaromatic group substituent is independently chosen for eachoccurrence from: (1) a lengthening agent L; (2) —COOX₁ or —C(O)X₆; (3)aryl, haloaryl, C₃-C₁₀ cycloalkylaryl, and an aryl group that is mono-or di-substituted with C₁-C₁₈ alkyl or C₁-C₁₈ alkoxy; (4) C₁-C₁₈ alkyl,C₃-C₁₀ cycloalkyl, C₃-C₁₀ cycloalkyloxy(C₁-C₁₈)alkyl, aryl(C₁-C₁₈)alkyl,aryloxy(C₁-C₁₈)alkyl, mono- or di-(C₁-C₁₈)alkylaryl(C₁-C₁₈)alkyl, mono-or di-(C₁-C₁₈)alkoxyaryl(C₁-C₁₈)alkyl, C₁-C₁₈ haloalkyl, andmono(C₁-C₁₈)alkoxy(C₁-C₁₈)alkyl; (5) C₁-C₁₈ alkoxy, C₃-C₁₀ cycloalkoxy,cycloalkyloxy(C₁-C₁₈)alkoxy, aryl(C₁-C₁₈)alkoxy, aryloxy(C₁-C₁₈)alkoxy,mono- or di-(C₁-C₁₈)alkylaryl(C₁-C₁₈)alkoxy, and mono- ordi-(C₁-C₁₈)alkoxyaryl(C₁-C₁₈)alkoxy; (6) aminocarbonyl,aminocarbonyl(C₁-C₁₈)alkylene, amino, mono- or di-alkylamino,diarylamino, piperazino, N—(C₁-C₁₈)alkylpiperazino, N-arylpiperazino,aziridino, indolino, piperidino, morpholino, thiomorpholino,tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidyl, hydroxy,acryloxy, methacryloxy, and halogen; (7) —OX₇ or —N(X₇)₂; (8) —SX₁₁; (9)a nitrogen containing ring represented by Formula i; (10) a grouprepresented by Formula ii or iii; (11) an unsubstituted ormono-substituted group chosen from pyrazolyl, imidazolyl, pyrazolinyl,imidazolinyl, pyrrolidinyl, phenothiazinyl, phenoxazinyl, phenazinyl, oracridinyl, wherein each substituent is independently chosen from alengthening agent L, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, phenyl, hydroxy, aminoor halogen; (12) a group represented by Formula iv or v:

wherein: (I) V′ is independently chosen in each formula from —O—, —CH—,C₁-C₆ alkylene, and C₃-C₁₀ cycloalkylene, (II) V is independently chosenin each formula from —O— or —N(X₂₁)—, wherein X₂₁ is a lengthening agentL, hydrogen, C₁-C₁₈ alkyl, and C₂-C₁₈ acyl, provided that if V is—N(X₂₁)—, V′ is —CH₂—, (III) X₁₈ and X₁₉ are each independently chosenfrom a lengthening agent L, hydrogen and C₁-C₁₈ alkyl, and (IV) k ischosen from 0, 1, and 2, and each X₂₀ is independently chosen for eachoccurrence from a lengthening agent L, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy,hydroxy and halogen; or (13) a group represented by Formula vi:

wherein (I) X₂₂ is chosen from a lengthening agent L, hydrogen andC₁-C₁₈ alkyl, and (II) X₂₃ is chosen from a lengthening agent L and anunsubstituted, mono-, or di-substituted group chosen from naphthyl,phenyl, furanyl and thienyl, wherein each substituent is independentlychosen for each occurrence from C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, andhalogen; (D) provided that when said photochromic material isrepresented by graphic formula IVA or IVB, Q independently comprises foreach occurrence-N₃; or —CCR′, provided that the indolino group issubstantially free of N-substituents; or —OSO₂R′″, provided that saidphotochromic material is substantially free of carbonyl groups and eachR″ is independently chosen for each occurrence from hydrogen, asubstituted or unsubstituted alkyl, cycloalkyl, arylalkyl, or togetherform cycloalkyl that is substituted or unsubstituted; and R and i arethe same as hereinbefore; and (E) provided that when said photochromicmaterial is represented by graphic formula VI, Q comprises: —N₃, —CN,—CCR′, or —OSO₂R′″; E is —O— or —N(Q)-; and D is represented by thefollowing graphic formula:

 wherein: T is —S—, —O— or —N(R)—, J is a spiro-alicyclic ring and Q isthe same as described hereinbefore.
 2. (canceled)
 3. A photochromiccomposition comprising the photochromic material of claim 1 incorporatedinto at least a portion of an organic material, said organic materialbeing a polymeric material, an oligomeric material, a monomeric materialor a mixture or combination thereof.
 4. The photochromic composition ofclaim 3, wherein said polymeric material comprises self-assemblingmaterials, polycarbonate, polyamide, polyimide, poly(meth)acrylate,polycyclic alkene, polyurethane, poly(urea)urethane, polythiourethane,polythio(urea)urethane, polyol(allyl carbonate), cellulose acetate,cellulose diacetate, cellulose triacetate, cellulose acetate propionate,cellulose acetate butyrate, polyalkene, polyalkylene-vinyl acetate,poly(vinylacetate), poly(vinyl alcohol), poly(vinyl chloride),poly(vinylformal), poly(vinylacetal), poly(vinylidene chloride),poly(ethylene terephthalate), polyester, polysulfone, polyolefin,copolymers thereof, and/or mixtures thereof.
 5. The photochromiccomposition of claim 3, wherein the photochromic composition furthercomprises at least one additive chosen from dyes, alignment promoters,kinetic enhancing additives, photoinitiators, thermal initiators,polymerization inhibitors, solvents, light stabilizers, heatstabilizers, mold release agents, rheology control agents, levelingagents, free radical scavengers, gelators and adhesion promoters.
 6. Thephotochromic composition of claim 3, comprising a coating compositionchosen from self-assembling materials and film forming materials.
 7. Aphotochromic article comprising a substrate and a photochromic materialaccording to claim 1 connected to at least a portion of a substrate. 8.The photochromic article of claim 7, comprising an optical element, saidoptical element being at least one of an ophthalmic element, a displayelement, a window, a mirror, packaging material and an active or passiveliquid crystal cell element.
 9. The photochromic article of claim 8,wherein the ophthalmic element comprises corrective lenses,non-corrective lenses, contact lenses, intra-ocular lenses, magnifyinglenses, protective lenses, or visors.
 10. The photochromic article ofclaim 8, wherein the display element comprises screens, monitors andsecurity elements.
 11. The photochromic article of claim 7, wherein thesubstrate comprises a polymeric material and the photochromic materialis incorporated into at least a portion of the polymeric material. 12.The photochromic article of claim 11, wherein the photochromic materialis blended with at least a portion of the polymeric material, bonded toat least a portion of the polymeric material, and/or imbibed into atleast a portion of the polymeric material.
 13. The photochromic articleof claim 7, wherein the photochromic article comprises a coating or filmconnected to at least a portion of the substrate, said coating or filmcomprising the photochromic material.
 14. The photochromic article ofclaim 13, wherein said substrate is formed from organic materials,inorganic materials, or combinations thereof.
 15. The photochromicarticle of claim 12, further comprising at least one additional at leastpartial coating chosen from photochromic coatings, anti-reflectivecoatings, linearly polarizing coatings, transitional coatings, alignmentlayers, primer coatings, adhesive coatings, mirrored coatings andprotective coatings including antifogging coatings, oxygen barriercoatings and ultraviolet light absorbing coatings. 16-18. (canceled)